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    • 专利摘要:
    organopolysiloxane. the present invention provides an organopolysiloxane obtained by binding to at least two silicon atoms of an organopolysiloxane segment that constitutes a main chain, a poly (n-acylalkyleneimine) segment comprising a repeating unit represented by the following formula (1): in that r ^ 1 ^ represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms and n represents 2 or 3, through an alkylene group containing a heteroatom, where the poly (n-acylalkyleneimine) segment has a molecular weight numerical average of 1,600 to 3,500; a weight ratio of (a / b) of the organopolysiloxane segment (a) that constitutes the backbone for the poly (n-acylalkyleneimine) segment (b) (hereinafter simply referred to as the (a / b) weight ratio)) is 42/58 and 58/42; the organopolysiloxane segment between two poly (n-acylalkyleneimine) segments adjacent to each other has an average molecular weight of 1,600 to 3,500 and the organopolysiloxane segment that constitutes the main chain has an average molecular weight of 7,000 to 100,000.
    公开号:BR112012007678B1
    申请号:R112012007678
    申请日:2010-11-08
    公开日:2019-12-24
    发明作者:Fukuhara Kazuhisa；Tada Kiyotake；Tejima Noriko；Kobaru Shuichiro；Kodate Takashi
    申请人:Kao Corp；
    IPC主号:
    专利说明:

    ORGANOPOLYSILOXAN
    FIELD OF THE INVENTION
    The present invention relates to an organopolysiloxane having a specific structure.
    BACKGROUND OF THE INVENTION
    Since organopolysiloxanes have many excellent characteristics, organopolysiloxanes have been used, in various forms, frequently as a sensation enhancer or as a film-forming resin. For example, Patent Document 1 describes an organopolysiloxane modified with poly (Nacylalkyleneimine) having a high modulus of elasticity and not subject to breakage or plastic deformation within a given range of extensibility. According to such a document, this organopolysiloxane is excellent, for example, in the shaping performance of the hair and the fixing property of the hair thus modeled in comparison with conventional film-forming resins.
    Prior Art Document
    Patent Document:
    Patent Document 1 - JP-A 07-133352
    SUMMARY OF THE INVENTION
    The present invention provides an organopolysiloxane obtained by binding to at least two silicon atoms of an organopolysiloxane segment that constitutes a main chain, a poly (N-acylalkyleneimine) segment comprising a repeating unit represented by the following formula (1) :
    where R 1 represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms and n is 2 or 3, through an alkylene group containing a heteroatom, where the poly (N-acylalkyleneimine) segment has an average molecular weight numeric from 1,600 to 3,500; a mass ratio (a / b) of the organopolysiloxane segment (a) that constitutes the main chain for the poly (N-acylalkyleneimine) segment (b) (hereinafter simply called mass ratio (a / b)) is 42 / 58 to 58/42; the organopolysiloxane segment between two poly (N-acylalkyleneimine) segments adjacent to each other has an average molecular weight of 1,600 to 3,500 and the organopolysiloxane segment that constitutes the main chain has an average molecular weight of 7,000 to 100,000.
    DETAILED DESCRIPTION OF THE INVENTION
    When the organopolysiloxane described in Patent Document 1 is used, for example,
    Petition 870190106057, of 10/21/2019, p. 7/25
    2/14 For example, in a hair styling agent, the resulting hair styling agent is excellent in fixation performance, since it has a high modulus of elasticity. However, the present organopolysiloxane does not perform well in the volume of deformation within which the deformation occurs without causing breakage or plastic deformation, so that the great deformation of the hair due to external factors (using the fingers to comb the hair, wind, oscillations or the like) can result in the breakage or deformation of a film formed on the hair. Thus, it does not perform sufficiently in terms of maintaining a hairstyle for several hours.
    The present inventors carried out an extensive investigation and found that an organopolysiloxane that has a specific structure has a high modulus of elasticity with a large volume of deformation within which deformation occurs without causing rupture or plastic deformation, so that it presents excellent properties like an elastomer.
    The present invention provides an organopolysiloxane with a high modulus of elasticity, as well as a large deformation volume (hereinafter called deformable volume) within which deformation occurs without causing rupture or plastic deformation.
    Organopolysiloxane
    The organopolysiloxane of the present invention is a polymer obtained by binding the poly (N-acylalkyleneimine) segment composed of a repeating unit represented by the above formula (1) to at least two silicon atoms in the organopolysiloxane segment that constitute the main chain through of an alkylene group containing a hetero atom.
    At least two poly (N-acylalkyleneimine) segments are attached to any of the silicon atoms that make up the organopolysiloxane segment through an alkylene group containing a hetero atom. It is preferred that they are attached to one or more silicon atoms of the organopolysiloxane segment except for those at both ends of the same, via the alkylene group and, more preferred, that they are attached to two or more silicon atoms of the segment organopolysiloxane except for those at both ends through the alkylene group. This means that the organopolysiloxane of the present invention is a graft polymer having, as a side chain thereof, at least two segments of poly (N-acylalkyleneimine), each composed of a repeating unit represented by the formula (1) above.
    The alkylene group containing a heteroatom functions as a linking group for the poly (N-acylalkyleneimine) segment. Examples of such an alkylene group include alkylene groups having 2 to 20 carbon atoms and containing 1 to 3 nitrogen atoms, oxygen atoms, or sulfur atoms. Among them, the groups represented by
    Petition 870190106057, of 10/21/2019, p. 8/25
    3/14 any of the following formulas (i) to (vii) are preferred, of which those represented by formula (i) or (ii) are most preferable and those which are represented by formula (i) are most preferable. In the formula, An ~ represents a counterion of a quaternary ammonium salt and its examples include ethyl sulfate ions, methyl sulfate ions, chloride ions, iodide ions, sulfate ions, p-toluenesulfonate ions and perchlorate ions.
    - (CH ^ NH (i) —NH - (· CH ^ NH— (jj) ch 3 , 4 | An —fcH 2 W— (iü) ch 3 Ç H 3 An- - (cH 2 - ^ - N - (- CH 2 - ^ - N (IV) ch 3 ch 3 | An '/ CH 3 - (c ^ N ^ CH ^ N CH, CH 3 ch 3 l + An (V) - (oH 2 ^ -O — CH 2 ÇHCH 2 —--- (vi) OH CH 3
    —FcH ^ S— (vü)
    In the N-acylalkyleneimine unit constituting the poly (Nacylalkyleneimine) segment, the alkyl group having 1 to 3 carbon atoms represented by R 1 in formula (1) is, for example, a linear alkyl group having 1 to 3 carbons atoms or a branched alkyl group having 3 carbon atoms. Specific examples of these include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
    In formula (1), n is the number 2 or 3 and is preferably 2, from the point of view of availability of raw materials for the preparation of the organopolysiloxane of the present invention.
    The organopolysiloxane of the present invention can achieve both a high modulus of elasticity and a large deformable volume as the mass ratio (a / b) falls within a range of 42/58 to 58/42. From this point of view, the weight ratio (a / b) is preferably 45/55 to 55/45, more preferably 47/53 to 53/47.
    The term mass ratio (a / b) as used in this document means a value determined from an integral proportion of the alkyl or phenyl group in the organopolysiloxane segment to the methylene group in the poly (Nacylalkyleneimine) segment, found by bonding a solution that was obtained by dissolving
    5% by weight of the organopolysiloxane of the present invention in deuterated chloroform, for analysis of nuclear magnetic resonance ( 1 H-NMR). The organopolysiloxane of the present invention showing the mass ratio (a / b) within the range described above is excellent in solubility in a polar solvent, such as, water and easy handling after dissolution therein.
    When in the organopolysiloxane of the present invention, the organopolis segment Petition 870190106057, of 10/21/2019, p. 9/25
    4/14 siloxane between two poly (N-acylalkyleneimine) segments adjacent to each other has a weight average molecular weight (hereinafter simply MWg) within a range of 1,600 to 3,500, the resulting organopolysiloxane can have a large deformable volume. From this point of view, MWg is more preferably from 1,800 to 3,200, even more preferably from 2,000 to 3,000.
    The term organopolysiloxane segment between the poly (Nacylalkyleneimine) segments adjacent to each other as used in this document, means, as represented by formula (2), a segment surrounded by a dotted line between two points of a connection point (point a) of a poly (N-acylalkyleneimine) segment to the organopolysiloxane segment at a connection point (β) of a poly (N-acylalkyleneimine) segment adjacent to the poly (Nacylalkyleneimine) segment described above and composed of one unit of R 2 SiO, one R 6 , and fractions y +1 of the units (R 2 ) 2S1O. The term "poly (N-acylalkyleneimine) segment" means attachment of -WR 7 to R 6 .
    In the formula (2) above, R 2 independently represents an alkyl group having from 1 to 22 carbon atoms or a phenyl group, R 6 represents an alkylene group containing a heteroatom, -WR 7 represents a poly (N-acylalkyleneimine) segment , R 7 represents a residue from a polymerization initiator, and Y is a positive number.
    MMg is the molecular weight of the segment surrounded by a dotted line in the formula (2) above and can be understood as mass (g / mol) of the organopolysiloxane segment per mol of the poly (N-acylalkyleneimine) segment. When one hundred percent of the functional group of a modified organopolysiloxane that is a raw material compound is replaced with poly (N-acylalkyleneimine), the value will be equal to the functional group equivalent (g / mol) of the modified organopolysiloxane.
    The molecular weight of the poly (N-acylalkyleneimine) segment can be calculated from the molecular weight and degree of polymerization of an N-acylalkyleneimine unit or measured using gel permeation chromatography (hereinafter simply called GPC). In the present invention, molecular weight means the numerical average molecular weight, in terms of polystyrene (hereinafter referred to simply as MNox) as determined by measurement by GPC conducted under measurement conditions described further ahead, 870190106057, of 21/10/2019, pg. 10/25
    5/14 te in the Examples. When MNox falls within the range of 1,600 to 3,500, an organopolysiloxane exhibiting a large deformable volume can be obtained. From this point of view, the
    MNox is preferably from 1,800 to 3,200, more preferably from 2,000 to 3,000, even more preferably from 2,000 to 2,500.
    MMg can be calculated from the following formula (I), using the content (% by mass) (hereinafter simply called CSI) of the organopolysiloxane segment that constitutes the main chain.
    MMg = Csi x MNox / (100-Csi) (I)
    The average molecular weight (hereinafter simply referred to as MMsi) of the organopolysiloxane segment that forms the main chain is 7,000 to 100,000. From the point of view of solubility in a polar solvent such as water and ease of handling after its dissolution, it is preferably from 10,000 to 80,000, more preferably from 20,000 to 60,000, more preferably from 20,000 to 50,000, even more preferably from 20,000 to 40,000. The organopolysiloxane of the present invention can be easily incorporated into various products by dissolving it in a polar solvent, such as water. The organopolysiloxane segment that constitutes the main chain has a skeleton common to a modified organopolysiloxane which is a raw material compound, so that MMsi has an average molecular weight substantially equal to that of the modified organopolysiloxane which is a raw material compound. It should be noted that the average molecular weight of the modified organopolysiloxane which is a raw material compound is measured using GPC under the measurement conditions described in the Examples, and is expressed in terms of polystyrene.
    The average molecular weight (which will hereinafter simply be called MMt) of the organopolysiloxane of the present invention is preferably from 20,000 to 100,000, more preferably from 30,000 to 80,000, even more preferably from 40,000 to 80,000 from the point of view of solubility in a polar solvent such as water and ease of handling after dissolving it. MMt is determined using GPC under the measurement conditions described in the Examples, and is expressed in terms of polystyrene.
    The organopolysiloxane of the present invention has, in addition to a high modulus of elasticity and a large deformable volume, characteristic thermoplasticity, which means that when heated to a temperature range of 50 to 22 ° C, it shows markedly improved plasticity and smoothness , however, while the temperature returns to the ambient temperature after the end of heating, it restores elasticity quickly.
    Organopolysiloxane Preparation Process
    A process for preparing the organopolysiloxane of the present invention will be described below.
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    6/14
    The organopolysiloxane of the present invention is prepared, for example, by reacting a modified organopolysiloxane represented by the following formula (3):
    where R 2 has the same meaning as described above, R 3 and R 4 independently represent the same group as R 2 or a monovalent group represented by any of the following formulas (viii) to (xiii):
    fcH 2 - ^ - NH 2 (viii) --- fcH ^ NH-fCH ^ N ^ (ix) (CH ^ NÍCHah (x) (cH ^ N ^ CH ^ NICH) ;, (xi)ch 3 {• CH 2 ) yO — CH 2 CHCH 2 —N (CH 3 ) 2 (xii) --- £ cH 2 - ^ - SH (xiü)
    OH
    R 5 represents a monovalent group according to any of the formulas above (viii) (xiii), d represents the number from 91.5 to 1,255.0, and e represents the number from 2.0 to 62.5, with a poly (N-acylalkyleneimine) terminal reaction that can be obtained by ring-opening polymerization of a cyclic imino-ether represented by formula (4)
    Follow:( <(CH 2 ) n ^ = cJ <4)
    where R 1 and n have the same meanings as described above.
    In the ring-opening polymerization of the cyclic imino-ether represented by formula (4) (hereinafter simply called cyclic imino-ether (4)), a polymerization initiator can be used. Alkyl esters of a strong acid can be used as the polymerization initiator, compounds having high electrophilic reactivity. Examples of these include alkyl benzene sulfonate ester, alkyl p-toluene sulfonate ester, alkyl trifluoromethane sulfonate ester, alkyl trifluoracetate ester and dialkyl sulfate ester. Of these, the dialkyl sulfate ester is preferred.
    Examples of a solvent for polymerization include acetic acid esters, such as, ethyl acetate and propyl acetate, ethers, such as, diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran, ketones, such as, acetone and methyl ethyl ketone, halogenated solvents, such as chloroform and methylene chloride, nitrile-based solvents such as acetonitrile and benzonitrile, and polar aprotic solvents such as N, NPetition 870190106057, 10/21/2019, p. 12/25
    7/14 dimethylformamide, Ν, Ν-dimethylacetamide, and dimethyl sulfoxide. Of these, acetic acid esters are preferred. The amount of solvent used is generally 20 to 2,000 parts by weight based on 100 parts by weight of the cyclic imino ether (4).
    The polymerization temperature is typically 30-170 ° C, preferably 40 to 150 ° C. The polymerization time varies depending on the polymerization temperature or the like and is typically from 1 to 60 hours.
    The use of substituted 2-oxazoline 2, for example, as the cyclic imino ether (4) provides poly (N-acylethyleneimine), which is a compound of the above formula (1) having 2 as n, although the use of dihydro- 2-oxazine substituted 2 provide poly (Nacylpropyleneimine), which is a compound of the above formula (1) having 3 as n.
    The poly (N-acylalkyleneimine) that can be obtained by the controlled polymerization of cyclic imino-ether (4) has, at its end, a reactive group. Therefore, the organopolysiloxane of the present invention can be obtained by reacting the reactive group at the end of the poly (N-acylalkyleneimine) with the reactive group represented by any of the formulas above (viii) (xiii) which is presented by the modified organopolysiloxane represented by formula (3).
    The preparation process using controlled polymerization is effective in that it is possible to easily control the degree of polymerization with used amounts of the cyclic imino ether (4) and the polymerization initiator, as shown below in theoretical formula (II) and, furthermore, it is possible to obtain a substantially monodispersed poly (N-acylalkyleneimine) with a narrower molar weight distribution than that obtained by typical radical polymerization.
    MNi = number of moieties of cyclic imino-ether (4) number of mois of polymerization initiator x molecular weight of cyclic imino-ether (4) + molecular weight of polymerization initiator (II) (MNi: numerical average molecular weight calculated from poly (N-acylalkyleneimine) which can be obtained by controlled polymerization).
    The amount of cyclic imino ether (4) used and the amount of polymerization initiator used are preferably those providing the MNi in formula (II) from 1,600 to 3,500, more preferably from 1,800 to 3,200, even more preferably from 2,000 to 3,000.
    The average molecular weight of the modified organopolysiloxane represented by formula (3) is preferably from 7,000 to 100,000, more preferably from 10,000 to 80,000, more preferably from 20,000 to 60,000, more preferably from 20,000 to 50,000, even more preferably from 20,000 to 40,000 from the point of view of the solubility of the organopolysiloxane thus obtained in a polar solvent, such as water and ease
    Petition 870190106057, of 10/21/2019, p. 13/25
    8/14 handling after its dissolution.
    In addition, the equivalent functional group of the modified organopolysiloxane represented by formula (3) has an upper limit in order to satisfy both the mass ratio (a / b) and MMg of the organopolysiloxane of the present invention. From this point of view and in order to provide the main chain with the appropriate hydrophobicity, the equivalent functional group is preferably from 500 to 3,500, more preferably from 800 to 3,200, and even more preferably from 1,000 to 3,000. The term equivalent functional group of the modified organopolysiloxane represented by formula (3) means a value obtained by dividing the average weight molecular weight of the modified organopolysiloxane represented by formula (3) by an average of the number of R 5 per modified organopolysiloxane molecule.
    The modified organopolysiloxane represented by the formula (3) and the terminal reactive poly (Nacylalkyleneimine) are used in quantities to provide their weight ratios (modified reactive organopolysiloxane / poly (N-acylalkyleneimine)) within a preferred range of 42 / 58 to 58/42, more preferably from 45/55 to 55/45, even more preferably from 47/53 to 53/47 from the point of view of the modulus of elasticity and the deformable amount of organopolysiloxane thus obtained.
    Examples
    The present invention will now be described specifically on the basis of the examples. The present invention should not be limited by the Examples. In the synthesis of each organopolysiloxane, several molecular weights were measured according to the measurement conditions that follow.
    Conditions for measuring average molecular weight of modified organopolysiloxane
    Column: Super HZ4000 + Super ΗΖ2000 (product of Tosoh Corporation)
    Eluent: 1 mM triethylamine / THF
    Flow rate: 0.35 mL / minute
    Column temperature: 40 ° C
    Detector: UV
    Sample: 50 pL
    MNox and MMt measurement conditions
    Column: K-804L (product of Tosoh Corporation). Two columns connected in series.
    Eluent: 1 mM dimethyldodecylamine / chloroform
    Flow rate: 1.0 mL / minute
    Column temperature: 40 ° C
    Detector: RI
    Sample: 50 pL
    The 1 H-NMR measurement to determine the mass ratio (a / b) was conducted under the
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    9/14 following conditions.
    1H-NMR measurement conditions
    The polymer composition thus obtained was confirmed by 1 H-NMR (400 MHz, product from Varian, Inc.).
    A solution obtained by dissolving 0.5 g of a sample in 2 g of a solvent for measurement (deuterated chloroform) was measured.
    Pulse sequence:
    Relaxation delay: 30 seconds. Pulse: 45 degrees.
    Accumulated number: 8 times.
    Confirmed peaks: peak close to 0 ppm: polydimethylsiloxane methyl group, peak close to 3.4 ppm: methylene portion of ethylene imine.
    A silicone / poly (N-propionylethyleneimine) ratio was determined for each integral value.
    Example 1: Synthesis of Organopolysiloxane A
    A terminal reactive poly (N-propionylethyleneimine) was synthesized by dissolving
    6.17 g (0.04 mol) of diethyl sulfate and 93.8 g (0.947 mol) of 2-ethyl-2-oxazoline in 203 g of dehydrated ethyl acetate and heating the resulting solution under reflux for 8 hours in an atmosphere nitrogen. It had MNox of 2,500 as measured with GPC. A 33% ethyl acetate solution in 100 g of polydimethylsiloxane modified with primary side chain aminopropyl (average molecular weight: 26,000, equivalent amine (equivalent functional group): 2,000) was added at once and the resulting mixture was heated under reflux for 10 hours. The solvent was removed from the reaction mixture under reduced pressure to obtain organopolysiloxane A as a pale yellow solid. The resulting product had a weight ratio (a / b) of 50/50 and MMt of 56,000. The neutralization titration with hydrochloric acid while using methanol as the solvent revealed that about 20 mol% of the amino groups remained.
    Example 2: Synthesis of Organopolysiloxane B
    A terminal reactive poly (N-propionylethyleneimine) was synthesized by dissolving
    6.18 g (0.04 mol) of diethyl sulfate and 75.6 g (0.762 mol) of 2-ethyl-2-oxazoline in 166 g of dehydrated ethyl acetate and heating the resulting solution under reflux for 8 hours in an atmosphere nitrogen. It presented MNox of 2,040 as measured with GPC. A 33% ethyl acetate solution in 100 g of polydimethylsiloxane modified with primary side chain aminopropyl (average molecular weight: 46,000, equivalent amine (equivalent functional group): 1,870) was added at once and the resulting mixture was heated under reflux for 10 hours. The solvent was removed from the reaction mixture under reduced pressure to obtain organopolysiloxane B as a pale yellow solid. It presented a mass ratio (a / b) of 55/45 and MMt of 74,000. THE
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    10/14 neutralization titration with hydrochloric acid while using methanol as solvent revealed that about 25% in moieties of amino groups remained.
    Example 3: Synthesis of Orqanopolysiloxane C
    A terminal reactive poly (N-propionylethyleneimine) was synthesized by dissolving 7.22 g (0.05 mol) of diethyl sulfate and 110.2 g (1.11 mol) of 2-ethyl-2-oxazoline in 238 g of dehydrated ethyl acetate and heating the resulting solution under reflux for 8 hours in a nitrogen atmosphere. It had MNox of 2,500 as measured with GPC. A 33% ethyl acetate solution in 100 g of polydimethylsiloxane modified with primary side chain aminopropyl (average molecular weight: 26,000, equivalent amine (equivalent functional group): 2,000) was added at once and the resulting mixture was heated under reflux for 10 hours. The solvent was removed from the reaction mixture under reduced pressure to obtain organopolysiloxane C as a pale yellow solid. It presented a mass ratio (a / b) of 46/54 and MMt of 44,000. The neutralization titration with hydrochloric acid while using methanol as the solvent revealed that about 4% in moieties of amino groups remained.
    Example 4: Synthesis of Organopolysiloxane D
    A terminal reactive poly (N-propionylethyleneimine) was synthesized by dissolving 6.10 g (0.04 mol) of diethyl sulfate and 93.9 g (0.95 mol) of 2-ethyl-2-oxazoline in 203 g of dehydrated ethyl acetate and heating the resulting solution under reflux for 8 hours in a nitrogen atmosphere. It had a MNox of 2,530 as measured with GPC. A 33% ethyl acetate solution in 100 g of polydimethylsiloxane modified with primary side chain aminopropyl (average molecular weight: 46,000, equivalent amine (equivalent functional group): 1,870) was added at once and the resulting mixture was heated under reflux for 10 hours. The solvent was removed from the reaction mixture under reduced pressure to obtain organopolysiloxane D as a pale yellow solid. It presented a weight ratio (a / b) of 50/50 and MMt of 53,000. The neutralization titration with hydrochloric acid while using methanol as the solvent revealed that about 26% in moieties of amino groups remained.
    Comparative Example 1: Synthesis of Organopolysiloxane E
    A terminal reactive poly (N-propionylethyleneimine) was synthesized by dissolving 3.84 g (0.02 mol) of diethyl sulfate and 96.2 g (0.97 mol) of 2-ethyl-2-oxazoline in 203 g of dehydrated ethyl acetate and heating the resulting solution under reflux for 8 hours in a nitrogen atmosphere. It presented MNox of 4,000 as measured with GPC. A 33% ethyl acetate solution in 100 g of polydimethylsiloxane modified with primary side chain aminopropyl (average molecular weight: 26,000, equivalent amine (equivalent functional group): 2,000) was added at once and the resulting mixture was heated under reflux for 10 hours. The solvent was removed from the mixture
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    11/14 reaction under reduced pressure to obtain organopolysiloxane E as a pale yellow solid. It presented a mass ratio (a / b) of 50/50 and MMt of 100,000. The neutralization titration with hydrochloric acid while using methanol as a solvent revealed that about 49% in moieties of amino groups remained.
    Comparative Example 2: Synthesis of Organopolysiloxane F
    A terminal reactive poly (N-propionylethyleneimine) was synthesized by dissolving 9.10 g (0.06 mol) of diethyl sulfate and 141 g (1.42 mol) of 2-ethyl-2-oxazoline in 304 g of acetate of dehydrated ethyl and heating the resulting solution under reflux for 8 hours in a nitrogen atmosphere. It presented MNox of 2,540 as measured with GPC. A solution of 33% ethyl acetate in 100 g of polydimethylsiloxane modified with primary side chain aminopropyl (average molecular weight: 46,000, equivalent amine (equivalent functional group): 1,440) was added at once and the resulting mixture was heated under reflux for 10 hours. The solvent was removed from the reaction mixture under reduced pressure to obtain organopolysiloxane F as a pale yellow solid. It presented a mass ratio (a / b) of 40/60 and MMt of 100,000. The neutralization titration with hydrochloric acid while using methanol as the solvent revealed that about 15% in moieties of amino groups remained.
    Comparative Example 3: Synthesis of Organopolysiloxane G
    A terminal reactive poly (N-propionylethyleneimine) was synthesized by dissolving 11.8 g (0.08 mol) of diethyl sulfate and 88.2 g (0.89 mol) of 2-ethyl-2-oxazoline in 203 g of dehydrated ethyl acetate and heating the resulting solution under reflux for 8 hours in a nitrogen atmosphere. It had a MNox of 1,310 as measured with GPC. A solution of 33% ethyl acetate in 100 g of polydimethylsiloxane modified with primary side chain aminopropyl (average molecular weight: 10,000, equivalent amine (equivalent functional group): 1,090) was added at once and the resulting mixture was heated under reflux for 10 hours. The solvent was removed from the reaction mixture under reduced pressure to obtain organopolysiloxane G as a pale yellow solid. It presented a mass ratio (a / b) of 50/50 and MMt of 23,000. The neutralization titration with hydrochloric acid while using methanol as the solvent revealed that about 17% in moieties of amino groups remained.
    Comparative Example 4: Synthesis of Organopolysiloxane H
    A terminal reactive poly (N-propionylethyleneimine) was synthesized by dissolving 3.77 g (0.02 mol) of diethyl sulfate and 57.5 g (0.58 mol) of 2-ethyl-2-oxazoline in 124 g of dehydrated ethyl acetate and heating the resulting solution under reflux for 8 hours in a nitrogen atmosphere. It had a MNox of 2,510 as measured with GPC. A 33% ethyl acetate solution in 100 g of polydimethylsiloxane modified with primary side chain aminopropyl (average molecular weight: 26,000,
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    12/14 equivalent amine (equivalent functional group): 2,000) was added at once and the resulting mixture was heated under reflux for 10 hours. The solvent was removed from the reaction mixture under reduced pressure to obtain organopolysiloxane H as a pale yellow solid. It presented a mass ratio (a / b) of 62/38 and MMt of 65,000. The neutralization titration with hydrochloric acid while using methanol as a solvent revealed that about 50% in moieties of amino groups remained.
    Evaluation
    When using the organopolysiloxanes obtained in Examples 1 to 4 and Comparative Examples 1 to 4, as a sample, their elastic modules, extensibility and solubility in water were measured in accordance with the following methods. The results are collectively shown in Table 1.
    The samples to be used for measuring the modulus of elasticity and extensibility were prepared using the following film-forming process.
    Film Forming Process
    An adequate amount of an organopolysiloxane ethanol solution (50% by weight) was melted in a Teflon Petri dish (trademark) and dried for 5 days, draining nitrogen at room temperature. It was then dried under reduced pressure (40 kPa) while flowing nitrogen for 8 hours at room temperature to obtain a pale yellow transparent film about 1 mm thick. The film thus obtained was cut into pieces and the resulting pieces were used as a sample for the measurement of an elasticity and extensibility module.
    Measurement of the modulus of elasticity
    The modulus of elasticity of each sample was measured according to the following method. When the film has an elastic modulus of 5x10 6 Pa or more, the organopolysiloxane used as a hair styling agent has a high hair holding force.
    Devices used for measurement: DVA-225 dynamic viscoelasticity measuring device (product of IT Keisoku Seigyo Co, Ltd.)
    Measuring mode: Shear mode
    Resistance: from 0.01 to 0.1%
    Frequency: 1 Hz
    Sample size: (0.8 to 1.5) x (8 to 10) x (5 to 6) mm
    Measured at: 25 ° C
    Extensibility Measurement
    The term extensibility as used in this document means a ratio, in relation to an initial sample length (length before elongation), of a deformation volume of a ruptured sample, which is calculated from
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    13/14 according to the following equation (III) using a sample length at break in an elongation direction, as a result of sample elongation under the following measurement conditions and the initial sample length. When the sample has an extensibility of 50% or more, the film formed on the hair using the corresponding organopolysiloxane as a styling agent does not break easily, even due to great deformation of the hair due to external factors (using fingers to comb the hair, wind, oscillations or the like) and the styling of the hair thus fixed can be maintained for several hours.
    Extensibility (%) = (length of a sample at break in an elongation direction - initial sample length) / initial sample length (III)
    Device: Tensilon RTC (A&D Company product)
    Measuring mode: Elongation
    Sample size: (0.8 to 1.0) x (4.0 to 6.0) x (38.0-40.0) mm
    Measured at: 25 ° C
    Elongation rate: 300 mm / min
    Measurement of Water Solubility
    A 5% by weight aqueous solution or dispersion of each sample was prepared and the transmittance (% T) of the resulting liquid was measured according to the following conditions. The transmittance of 50% or more suggests easy incorporation of the sample in water.
    Device: UV-VIS spectrophotometer UV-2550 (product from Shimadzu Corporation)
    Measurement mode: transmittance
    Wavelength measurement: 660 nm
    Sample: 5% dispersion by weight in deionized water
    Optical path length: 1 cm
    Table 1:
    Example 5
    Example 6
    Example 7
    Example 8
    Ex.
    Ex.
    Ex.
    Ex.
    Organopolysiloxane
    Comp.
    Comp.
    Comp.
    Comp.
    MNox
    2,500
    2,040
    2,500
    2,530
    4,000
    2,540
    1,310
    2,510
    MWsi *
    26,000
    46,000
    2,6000
    46,000
    26.00
    46.00
    10.00
    26.00
    MWg
    2,500
    2,490
    2,080
    2,530
    4,000
    1,690
    1,310
    4,000
    Reason in
    50/50
    55/45
    46/54
    50/50
    50/50
    40/60
    50/50
    62/38 weight (a / b)
    Elastic module1x10 7
    8x10 6
    2x10 7
    2x10 7
    8x10 6
    3x10 7
    4x10 6
    2x10 6 dade (Pa)
    Petition 870190106057, of 10/21/2019, p. 19/25
    14/14
    Extensibility (%) 170 300 60 150 20 10 20 300 Transmittance (T%) 95 51 96 61 1 96 13 _ **
    *: Average molecular weight of the modified primary side chain of modified aminopropyl-polydimethylsiloxane was used.
    **: Not measured due to precipitation.
    The Examples and Comparative Examples of Table 1 clearly showed that the organopolysiloxanes of the present invention are excellent elastomers having a large deformable volume, while having a high modulus of elasticity. In addition, the organopolysiloxanes of the present invention have excellent solubility in water.
    权利要求:
    Claims (3)
    [1]
    1. Organopolysiloxane obtained by binding to at least two silicon atoms of an organopolysiloxane segment that constitutes a main chain, a poly (N-acylalkyleneimine) segment comprising a repeating unit represented by the formula (1) below:
    (1)
    CHARACTERIZED by the fact that R 1 represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms and n is 2 or 3, through an alkylene group containing a heteroatom, in which the poly (N-acylalkyleneimine) segment it has a numerical average molecular weight of 1,600 to 3,500; a mass ratio of (a / b) of the organopolysiloxane segment (a) that forms the backbone for the poly (N-acylalkyleneimine) segment (b) is 45/55 to 55/45; the organopolysiloxane segment between two poly (Nacylalkyleneimine) segments adjacent to each other has an average molecular weight of 1,600 to 3,500; and the organopolysiloxane segment that constitutes the main chain has an average molecular weight of 20,000 to 40,000, and in which the said organopolysiloxane is obtained by the reaction of the modified organopolysiloxane represented by the formula (3) below:

    R where R 2 has the same meaning as described above, R 3 and R 4 independently represent the same group as R 2 or a monovalent group represented by any of the formulas (viii) to (xiii) below:
    NH

    R 5 represents a monovalent group represented by any of the formulas (viii) to (xiii) above, d represents a number from 91.5 to 1255.0 and e represents a number from 2.0 to 62.5, with a poly ( Terminal reaction N-acylalkyleneimine) that can be obtained by
    Petition 870190106057, of 10/21/2019, p. 5/25
    [2]
    2/2 ring opening polymerization of a cyclic imino ether represented by the following formula (4):
    X (CH 2 ) n -x <) (4) v n = c — cr
    À 'where R 1 and n have the same meanings as described above.
    2. Organopolysiloxane, according to claim 1, CHARACTERIZED by the fact that among the silicon atoms of the organopolysiloxane segment that constitute the main chain, to which the poly (N-acylalkyleneimine) segment is linked through the alkylene group containing a heteroatom, one or more silicon atoms are different silicon atoms from those silicon atoms at both ends of the organopolysiloxane segment.
    [3]
    3. Organopolysiloxane according to claim 1 or 2, CHARACTERIZED by the fact that the alkylene group containing a heteroatom is an alkylene group having from 2 to 20 carbon atoms and containing from one to three nitrogen atoms, oxygen atoms or sulfur atoms.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS6242785Y2|1982-03-09|1987-11-02|
    JPS6242787Y2|1982-05-17|1987-11-02|
    JPS6242786Y2|1982-05-17|1987-11-02|
    EP0344688B1|1988-05-31|1993-08-04|Mitsubishi Kasei Corporation|Process for producing a phenolate and process for producing an aromatic polyether ketone employing it|
    JPH0670104B2|1988-12-09|1994-09-07|花王株式会社|Film-forming resin and hair cosmetic containing the same|
    JP2716831B2|1989-01-11|1998-02-18|花王株式会社|Novel organopolysiloxane and method for producing the same|
    JP2843101B2|1990-04-02|1999-01-06|花王株式会社|Cosmetics|
    JP2515452B2|1991-10-18|1996-07-10|花王株式会社|Cosmetics|
    DE69424100T2|1993-08-10|2000-10-12|Kao Corp|Organopolysiloxanes and a method of setting hair using the same|
    JPH07133352A|1993-08-10|1995-05-23|Kao Corp|Organopolysiloxane, hair-setting composition containing same, and setting method for hair using the same|
    JPH07173395A|1993-12-21|1995-07-11|Kao Corp|Gel composition|
    JP3583164B2|1994-05-25|2004-10-27|株式会社吉野工業所|Pump container for foam release|
    DE4426794C1|1994-07-28|1995-07-06|Goldwell Ag|Agent for treating damaged hairs which is easily washed out|
    JP3652426B2|1994-12-12|2005-05-25|株式会社吉野工業所|Foam discharge pump container|
    JP3215617B2|1995-02-21|2001-10-09|花王株式会社|Coating resin and hair cosmetic containing the same|
    JP3746848B2|1995-07-18|2006-02-15|三井化学株式会社|High molecular weight polyolefin microporous film and method for producing the same|
    TW408134B|1995-07-18|2000-10-11|Mitsui Chemicals Inc|Microporous film of high molecular weight polyolefin and process for producing same|
    JPH09143037A|1995-11-17|1997-06-03|Kao Corp|Hair cosmetic|
    JPH1019869A|1996-07-02|1998-01-23|Kao Corp|Determining method of monomer with pi electron|
    JPH10306163A|1997-03-06|1998-11-17|Kao Corp|Organopolysiloxane|
    US6027718A|1997-03-06|2000-02-22|Kao Corporation|Organopolysiloxanes|
    TW513309B|1998-07-01|2002-12-11|Kao Corp|Powder-based solid cosmetic composition and preparation process thereof|
    DE19848002A1|1998-10-17|2000-04-20|Goldschmidt Ag Th|Polypeptide-polysiloxane copolymers|
    GB9912073D0|1999-05-24|1999-07-21|Unilever Plc|Polysiloxane block copolymers in topical cosmetic and personal care compositions|
    JP2002053440A|2000-08-11|2002-02-19|Kao Corp|Washing composition|
    DE10205529A1|2002-02-11|2003-08-14|Kpss Kao Gmbh|Improved hair dyeing process uses direct dyes together with an organopolysiloxane bonded via an alkylene group to a poly-|
    JP4060663B2|2002-08-06|2008-03-12|花王株式会社|Method for producing O / W emulsion composition|
    JP2004083691A|2002-08-26|2004-03-18|Kao Corp|Wettability enhancer|
    JP3905471B2|2002-12-27|2007-04-18|花王株式会社|Wrinkle remover composition for textile products|
    US7001864B2|2003-03-18|2006-02-21|Tosoh Corporation|Catalyst composition for production of a polyurethane resin, and method for producing a polyurethane resin|
    JP4171333B2|2003-03-25|2008-10-22|花王株式会社|Oil-in-water multiphase emulsion composition|
    US8153108B2|2003-04-25|2012-04-10|Kao Corporation|Hair cosmetic product|
    JP4074607B2|2003-08-06|2008-04-09|花王株式会社|Aerosol cosmetics|
    DE602004028079D1|2003-08-06|2010-08-26|Kao Corp|Cosmetic aerosol composition|
    JP4469688B2|2004-08-31|2010-05-26|花王株式会社|Hair cosmetics|
    JP2006232736A|2005-02-25|2006-09-07|Kao Corp|Hair cosmetic|
    JP2007217372A|2006-02-17|2007-08-30|Kao Corp|Hair cosmetic|
    JP4832105B2|2006-02-22|2011-12-07|花王株式会社|Hair cosmetics|
    JP5384788B2|2006-12-08|2014-01-08|花王株式会社|Emulsified cosmetics|
    US20100139681A1|2007-05-31|2010-06-10|Kao Corporation|Hair cosmetic composition|
    JP5507044B2|2007-07-20|2014-05-28|花王株式会社|Hair cosmetics|
    TWI413530B|2007-07-20|2013-11-01|Kao Corp|Organopolysiloxane|
    JP5367963B2|2007-07-20|2013-12-11|花王株式会社|Hair cosmetics|
    JP5478005B2|2007-07-20|2014-04-23|花王株式会社|Organopolysiloxane|
    JP5128201B2|2007-08-07|2013-01-23|花王株式会社|Makeup base|
    JP5474319B2|2007-11-27|2014-04-16|花王株式会社|Hair cosmetics|
    JP5349908B2|2008-10-30|2013-11-20|花王株式会社|Hair cosmetics|
    JP5669370B2|2009-02-27|2015-02-12|花王株式会社|Aerosol hair conditioner|
    JP5462505B2|2009-03-18|2014-04-02|花王株式会社|Hair dyeing method|
    CN102481237A|2009-08-21|2012-05-30|花王株式会社|Hair dyeing method|
    TWI475051B|2009-11-18|2015-03-01|Kao Corp|Organic polysiloxane|TWI413530B|2007-07-20|2013-11-01|Kao Corp|Organopolysiloxane|
    JP5645840B2|2008-12-02|2014-12-24|株式会社Ｗａｖｅ Ｌｉｆｅ Ｓｃｉｅｎｃｅｓ Ｊａｐａｎ|Method for synthesizing phosphorous atom-modified nucleic acid|
    SG10201403841QA|2009-07-06|2014-09-26|Ontorii Inc|Novel nucleic acid prodrugs and methods of use thereof|
    TWI475051B|2009-11-18|2015-03-01|Kao Corp|Organic polysiloxane|
    JP5663289B2|2009-12-16|2015-02-04|花王株式会社|Method for producing organopolysiloxane compound|
    JP5791335B2|2010-04-07|2015-10-07|花王株式会社|Method for producing organopolysiloxane compound|
    EP2620428B1|2010-09-24|2019-05-22|Wave Life Sciences Ltd.|Asymmetric auxiliary group|
    EP2647367B1|2010-11-30|2018-01-03|Kao Corporation|Hair cosmetic|
    EP2734208B1|2011-07-19|2017-03-01|Wave Life Sciences Ltd.|Methods for the synthesis of functionalized nucleic acids|
    JP5808183B2|2011-07-20|2015-11-10|花王株式会社|Hair cosmetics|
    WO2014002707A1|2012-06-25|2014-01-03|花王株式会社|Organopolysiloxane graft polymer|
    PT2872485T|2012-07-13|2021-03-05|Wave Life Sciences Ltd|Asymmetric auxiliary group|
    JP6071491B2|2012-12-03|2017-02-01|花王株式会社|Hair cosmetics|
    JP6378478B2|2013-02-13|2018-08-22|花王株式会社|Organopolysiloxane graft polymer|
    WO2015021516A1|2013-08-13|2015-02-19|L'oreal|Method for the treatment of hair from a composition comprising an organic mono acid and an aminosilicone|
    FR3009681B1|2013-08-13|2015-08-07|Oreal|PROCESS FOR TREATING KERATIN FIBERS FROM A HYDROALCOHOLIC COMPOSITION COMPRISING A MONO ORGANIC ACID|
    EP2868309B1|2013-10-31|2019-03-06|Kao Corporation|Hair styling composition|
    WO2015107425A2|2014-01-16|2015-07-23|Wave Life Sciences Pte. Ltd.|Chiral design|
    JP6328477B2|2014-04-25|2018-05-23|花王株式会社|Hairdressing cosmetics|
    JP2015209407A|2014-04-25|2015-11-24|花王株式会社|Hairdressing cosmetics|
    DK178227B1|2014-05-01|2015-09-07|Aquaporin As|A novel synthetic process of a block copolymer and a novel use|
    EP3275425B1|2016-07-26|2021-03-03|Kao Germany GmbH|Hair styling composition|
    EP3275424B1|2016-07-26|2020-12-02|Kao Germany GmbH|Composition to reduce the drying time of keratin fibers, method and use thereof|
    EP3311794A1|2016-10-19|2018-04-25|Kao Germany GmbH|Cosmetic composition comprising two optical brighteners, method, use, and kit-of-parts thereof|
    EP3329904A1|2016-12-05|2018-06-06|Kao Germany GmbH|Cosmetic composition for enhancing properties of pre-colored keratin fibers|
    JP2020026398A|2018-08-09|2020-02-20|花王株式会社|Method for producing coating film|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-03-19| B06T| Formal requirements before examination|
    2019-07-23| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-11-26| B09A| Decision: intention to grant|
    2019-12-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2009263402|2009-11-18|
    PCT/JP2010/069818|WO2011062077A1|2009-11-18|2010-11-08|Organopolysiloxane|
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