JP2017179146A - Polymer composite composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinked polymer easy to be pulverized while maintaining liquid absorption property.SOLUTION: There is provided a polymer composite composition containing a crosslinked polymer having a lactam structure. The polymer composite composition contains a crosslinked polymer (I) having a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure and a polymer (II) other than the crosslinked polymer (I).SELECTED DRAWING: None

Description

The present invention relates to a polymer composite composition. More specifically, a polymer composite composition suitably used for cosmetic applications such as surfactants, aromatic components, deodorant components, agrochemical components, liquid fertilizer components, cosmetic components and other support agents, moisturizers, thickeners, and dispersants. Related to things.

Polymers having a lactam structure are used in various cosmetics such as surfactants, volatile components, aromatic components, deodorant components, agricultural chemical components, liquid fertilizer components, cosmetic components, and other carriers, moisturizers, thickeners, dispersants, etc. It is blended. Patent Document 1 discloses a polyvinyl pyrrolidone aqueous solution for hair gel, which is a polyvinyl pyrrolidone aqueous solution for producing hair gel, which contains a tertiary amine and ammonia. Furthermore, Patent Document 2 discloses a gel composition in which at least one volatile component is supported on a gel made of polyvinyl lactams and polyalkyleneimines. Patent Document 3 discloses a composition containing a polyvinyl lactam and a polyalkyleneimine, wherein the aqueous solution has a cloud point.

It is also known that a polymer having a crosslinked structure is used as a water absorbent resin. In Patent Document 4, a monomer component essentially comprising a partially neutralized acid group-containing polymerizable monomer is added in an amount of 2 to 10% by weight with respect to the acid group-containing polymerizable monomer. Disclosed is a method for producing a water-absorbent resin characterized by polymerizing at a monomer component concentration of 31 wt% or more in the presence of ˜50 mol% of polyvinyl alcohol and a crosslinking agent, and further drying by heating at 150 ° C. or more. Has been.

International Publication No. 2008/096567 JP 2008-63481 A JP 2008-45004 A JP 7-228616 A

As described above, although the development of polymers having various lactam structures used in cosmetic applications and crosslinked polymers used in water-absorbing applications is being carried out, as the crosslinked polymer used in cosmetic applications, In order to increase the liquid absorption speed and to improve the feel and feel, a small particle size is required. In order to reduce the particle size, conventional crosslinked polymers must be repeatedly pulverized. There was a problem of not becoming.

This invention is made | formed in view of the said present condition, and it aims at providing the crosslinked polymer which is easy to grind | pulverize, maintaining liquid absorbency.

As a result of various studies on the crosslinked polymer, the present inventor has found that a polymer composite composition containing a crosslinked polymer having a lactam structure and a polymer different from the crosslinked polymer is easily pulverized while maintaining liquid absorption. As a result, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a polymer composite composition comprising a cross-linked polymer having a lactam structure, wherein the polymer composite composition is a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure. It is a polymer composite composition comprising a crosslinked polymer (I) having a polymer and a polymer (II) different from the crosslinked polymer (I).
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Polymer composite composition>
The polymer composite composition of the present invention comprises the crosslinked polymer (I) and a polymer (II) different from the crosslinked polymer (I). In the composition, the polymer (II) is It exists in the state which acts on crosslinked polymer (I). The polymer composite composition of the present invention includes those in a state where the polymer (II) acts on the crosslinked polymer (I), so that the polymer composite composition is more easily pulverized than the case of the crosslinked polymer (I) alone. . In the present invention, if the composition containing the crosslinked polymer (I) and the polymer (II) is a composition that is more easily pulverized than the crosslinked polymer (I) alone, the polymer (II) is crosslinked. It can be said that the polymer is in a state of acting on the polymer (I), and such a composition containing the crosslinked polymer (I) and the polymer (II) is defined as a polymer composite composition.
The polymer composite composition of the present invention contains the polymer (II) in a state of acting on the cross-linked polymer (I), so that it can be easily pulverized while sufficiently retaining the liquid absorption capacity of linoleic acid. Will improve. The reason why the pulverization is improved is as follows. The crosslinked polymer (I) has a structure in which the rings of the lactam structure are regularly arranged, and the crosslinked polymer (I) has high toughness by the interaction between the lactam rings. Therefore, it is considered that it is difficult to grind. On the other hand, the polymer composite composition of the present invention contains the crosslinked polymer (I) and the polymer (II), so that the polymer (II) is added to the crosslinked structure of the crosslinked polymer (I). It is considered that the interaction between the lactam rings is weakened. As a result, the toughness of the cross-linked polymer is reduced, so that it is considered that the cross-linked polymer is easily pulverized. Conventionally, when the crosslinked polymer is pulverized, the crosslinked polymer is frozen and pulverized with reduced toughness. However, the polymer composite composition of the present invention can be sufficiently pulverized even at room temperature. Therefore, pulverization can be performed more safely, and the cost can be reduced. The action of the crosslinked polymer (I) and the polymer (II) in the polymer composite composition of the present invention is any as long as the composition is more easily pulverized than the conventional crosslinked polymer. Although what may be sufficient, the effect | action which arises, for example by polymer (II) being entangled in the crosslinked structure of crosslinked polymer (I) is considered.

The polymer composite composition of the present invention is excellent in the ability to absorb linoleic acid by including the crosslinked polymer (I), and the absorbent capacity of linoleic acid per 1 g of the crosslinked polymer (I) is 10 g. The above is preferable. More preferably, the liquid absorption capacity is 12 g or more, further preferably 15 g or more, more preferably 20 g or more, still more preferably 30 g or more, particularly preferably 35 g or more, and most preferably 40 g or more. It is. The liquid absorption capacity of linoleic acid can be measured by the method described in the examples.

The polymer composite composition of the present invention is excellent in water absorption capacity by containing the crosslinked polymer (I), and the water absorption capacity per 1 g of the crosslinked polymer (I) is 10 g or more. Preferably there is. More preferably, the liquid absorption capacity is 13 g or more, more preferably 15 g or more, still more preferably 18 g or more, still more preferably 20 g or more, particularly preferably 23 g or more, and most preferably 25 g or more. It is. The water absorption capacity can be measured by the method described in the examples.

The content ratio of the crosslinked polymer (I) in the polymer composite composition of the present invention is preferably 80 to 99.99% by mass with respect to 100% by mass of the polymer composite composition. More preferably, it is 90-99.99 mass%, More preferably, it is 92-99.9 mass%, Most preferably, it is 95-99.5 mass%.

It is preferable that the content rate of polymer (II) in the polymer composite composition of this invention is 0.01-20 mass% with respect to 100 mass% of polymer composite compositions. More preferably, it is 0.05-10 mass%, More preferably, it is 0.1-8 mass%, Most preferably, it is 0.5-5 mass%.

The content ratio of the polymer (II) in the polymer composite composition of the present invention is preferably 0.01 to 25% by mass with respect to 100% by mass of the crosslinked polymer (I). More preferably, it is 0.01-15 mass%, More preferably, it is 0.01-10 mass%, More preferably, it is 0.05-10 mass%, Most preferably, it is 0.1-10 mass% Yes, most preferably 0.5-5% by mass.

The polymer composite composition of the present invention preferably has an average particle size of 0.1 μm to 200 μm. If the average particle diameter of the polymer composite composition is within the above preferred range, the surface area of the polymer composite composition will be in a suitable range, and the liquid absorption capability will be excellent. The average particle size of the polymer composite composition is more preferably 0.1 μm to 100 μm, and still more preferably 0.1 μm to 50 μm.
The average particle size of the polymer composite composition can be measured by a dry particle size distribution measuring device (Microtrack MT3000II series manufactured by Microtrack Bell Co., Ltd.).

(Crosslinked polymer (I))
The crosslinked polymer (I) contained in the polymer composite composition of the present invention has a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure.

The unsaturated monomer (A) having a lactam structure is a monomer having a lactam ring and an ethylenically unsaturated hydrocarbon group, and has the following formula (1);

(In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁴ > is the same or different, and represents the C1-C10 alkyl group which may have a hydrogen atom or a substituent. X is 0- It represents an integer of 4. y represents an integer of 1 to 3).
The number of carbon atoms of the alkyl group in the above ^R 1 to R ^4, 1 to 6, and more preferably from 1 to 4. The alkyl group is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
The substituent in the R ¹ to R ^4, although not particularly limited, ethylenically unsaturated hydrocarbon group; a carboxyl group, a sulfonic acid group and esters thereof and salts; amino group, a crosslinking agent such as a condensation reactable hydroxyl Reactive functional groups; and the like.
If at least one of R ^{1 to} R ⁴ in the unsaturated monomer (A) is a C 1-10 alkyl group having a reactive functional group capable of condensation reaction with the above-mentioned crosslinking agent as a substituent, A crosslinked structure can be formed by (2) and (3) described later.
R ^{1 to} R ³ are preferably hydrogen atoms. R ⁴ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
x is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and most preferably 0.
y is preferably 1 or 2, and more preferably 1.

Examples of the compound represented by the above formula (1) include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, 1- (2-propenyl) -2-pyrrolidone and the like. 1 type, or 2 or more types can be used. As the unsaturated monomer having a lactam structure, an unsaturated monomer having a pyrrolidone ring is preferable. More preferred is N-vinylpyrrolidone.

The crosslinked polymer (I) contained in the polymer composite composition of the present invention has a crosslinked structure in the structure. When the crosslinked polymer (I) has a crosslinked structure, (1) a single monomer containing a crosslinking monomer In the case of producing a polymer having a crosslinked structure by polymerizing a body component, (2) the reactive functional group is polymerized to a polymer obtained by polymerizing a monomer component containing a monomer having a reactive functional group. When a cross-linking agent having a plurality of functional groups that react with a group is reacted to form a cross-linked structure, (3) the monomer 1 having a reactive functional group and the reactive functional group of the monomer 1 react with After the monomer component including the monomer 2 having the reactive functional group to be polymerized is polymerized, the reactive functional group of the monomer 1 and the reactive functional group of the monomer 2 are reacted to crosslink In the case of forming a structure (self-crosslinking), (4) generating radicals in the polymer, If the formation (self-crosslinking), may form a (5) polymer to generate radical, by reacting a polymer and a crosslinkable monomer radicals occurs crosslinked structure.
The crosslinked structure of the crosslinked polymer (I) may be formed by any of the above (1) to (5), but is preferably formed by (1) above.

The crosslinkable monomer in the above (1) and (5) is as described later.
When the crosslinked polymer (I) has a crosslinked structure formed by the above (2) or (3), the crosslinked polymer (I) is an unsaturated monomer (A) having the lactam structure or As a structural unit derived from the other monomer (E) described later, a structural unit derived from a monomer having a reactive functional group is included.
Although it does not restrict | limit especially as a reactive functional group in said (2), (3), A carboxyl group, a sulfonic acid group, these esters and salts; An amino group, a hydroxyl group, etc. are mentioned.
When the crosslinked structure is formed by the above (3), the combination of reactive functional groups having reactivity with each other includes a carboxyl group (and its ester or salt), a hydroxyl group, and a sulfonic acid group (and its ester). And salts) and hydroxyl groups, carboxyl groups (and esters and salts thereof) and amino groups, sulfonic acid groups (and esters and salts thereof) and amino groups, and the like. A combination of a reactive functional group possessed by a monomer and a functional group reacting with the reactive functional group possessed by a crosslinking agent when the crosslinked structure of the polymer of the present invention is formed by the above (2) This example is the same as this.
The crosslinking agent in (2) is not particularly limited as long as it has a plurality of functional groups capable of reacting with the reactive functional group. For example, ethylenediamine, hexamethylenediamine, phenylenediamine, oxazoline group-containing polymer ( Nippon Shokubai Epocross), butanediol, tolylene diisocyanate, hexamethylene diisocyanate and the like.

The crosslinked polymer (I) may have a structural unit (e) derived from another monomer (E) other than the unsaturated monomer (A) having a lactam structure.
The other monomer (E) is not particularly limited as long as it can be copolymerized with the unsaturated monomer (A) having a lactam structure, and may be a crosslinkable monomer or a non-crosslinkable monomer. There may be.

When the crosslinked polymer (I) has a structural unit (e-1) derived from the crosslinkable monomer (E-1) as the other monomer (E), the above (1) or (5 ).
The crosslinkable monomer (E-1) is a compound having at least two polymerizable ethylenically unsaturated hydrocarbon groups per molecule, and preferably at least two radical polymerizable groups per molecule. This is a compound having an ethylenically unsaturated hydrocarbon group.
In addition, the compound which has a lactam structure and at least 2 ethylenically unsaturated hydrocarbon group shall be contained in the unsaturated monomer (A) which has a lactam structure, and a crosslinkable monomer.

Specific examples of the crosslinkable monomer (E-1) include N, N′-alkylenebis having an alkylene group having 1 to 4 carbon atoms such as N, N′-methylenebis (meth) acrylamide. (Meth) acrylamide; (poly) ethylene glycol di (meth) acrylate, (poly) alkylene glycol di (meth) acrylate having a C 1-4 alkylene group such as (poly) propylene glycol di (meth) acrylate; Tris that may be modified with alkylene oxides having 1 to 4 carbon atoms such as methylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate Methylolpropane (di, tri) (meth) acrylate Glycerin (di, tri) (meth) acrylate such as glycerol tri (meth) acrylate and glycerol acrylate methacrylate; Pentaerythritol (di, tri, tetra) (meth) acrylate such as pentaerythritol tetra (meth) acrylate; Dipentaerythritol such as erythritol hexa (meth) acrylate (di, tri, tetra, penta, hexa) (meth) acrylate; Pentaerythritol such as pentaerythritol tri (meth) allyl ether (di, tri, tetra) (Meth) allyl ether; triallyl compounds having 9 to 20 carbon atoms such as triallyl cyanurate (triallyl cyanurate), triallyl isocyanurate, triallyl phosphate, triallylamine; diallyl carbonate, 1,3-bis (a Diallyl compounds having 6 to 20 carbon atoms such as ryloxy) -2-propanol; (di, tri) vinyl compounds having 4 to 20 carbon atoms such as divinyl ether, divinyl ketone, and trivinylbenzene; tolylene diisocyanate, hexamethylene diisocyanate, etc. C2-20 diisocyanate; poly (meth) allyloxyalkane and the like. These may use only 1 type and may use 2 or more types together.
Among the crosslinkable monomers (E-1), it is preferable to use a compound having two or more allyl groups because the monomer having a remaining lactam structure and the soluble component tend to decrease. . Specifically, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine, diallyl carbonate, 1,3-bis (allyloxy) -2-propanol, pentaerythritol (di, tri, tetra) (meth) allyl Ethers are preferred, and triallyl cyanurate and pentaerythritol (di, tri, tetra) (meth) allyl ether are most preferred.

The polyalkylene glycol di (meth) acrylate preferably has 2 or more and 50 or less, more preferably 2 or more and 20 or less, and further preferably 2 or more and 10 or less oxyalkylene groups per molecule. It is preferable that an oxyethylene group is 50-100 mol% with respect to 100 mol% of oxyalkylene groups which the said polyalkylene glycol di (meth) acrylate has, and it is more preferable that it is 80-100 mol%.
One molecule of trimethylolpropane (di, tri) (meth) acrylate when the above trimethylolpropane (di, tri) (meth) acrylate is modified with an alkylene oxide having an alkylene group having 1 to 4 carbon atoms It is preferable that the average number of added alkylene oxides is the same.

As said other monomer (E), a non-crosslinkable monomer (E-2) will not be restrict | limited especially if it is a compound which does not have a lactam structure and has one ethylenically unsaturated hydrocarbon group. For example, (i) unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid and salts thereof; (ii) unsaturated dicarboxylic acids such as fumaric acid, maleic acid, methylene glutaric acid and itaconic acid and salts thereof (It may be a mono salt or a di salt); (iii) Unsaturated sulfonic acids such as 3-allyloxy-2-hydroxypropanesulfonic acid, (meth) allylsulfonic acid, isoprenesulfonic acid, and salts thereof (Iv) hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 3- (meth) allyloxy-1,2-dihydroxypropane, (meth) a Unsaturated alcohols such as alcohol, isoprenol and alkylene oxide adducts obtained by adding alkylene oxide to these hydroxyl groups; (v) methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as cyclohexyl acrylate; (vi) N-substituted such as (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, etc. Or unsubstituted (meth) acrylamide; (vii) vinyl aryl monomers such as styrene, indene and vinylaniline; (viii) alkenes such as ethylene, propylene, butadiene, isobutylene and octene; (ix) vinyl acetate and propion Vinyl acid, etc. (X) N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, vinyl pyridine, vinyl imidazole and salts thereof or quaternized products thereof. (Xi) vinylamides such as vinylformamide, vinylacetamide, vinyloxazolidone; (xii) unsaturated anhydrides such as maleic anhydride, itaconic anhydride; (xiii) vinylethylene carbonate and derivatives thereof; (xiv) Examples include (meth) acrylic acid-2-sulfonic acid ethyl ester and derivatives thereof; (xv) vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether.
These may use only 1 type and may use 2 or more types together.
Examples of the salts in the above (i) to (iii) and (x) include metal salts, ammonium salts, organic amine salts and the like. Examples of the alkylene oxide in the above (iv) include ethylene oxide, propylene oxide and the like, an alkylene oxide having 1 to 20 carbon atoms is preferable, and an alkylene oxide having 1 to 4 carbon atoms is more preferable. As addition mole number of the alkylene oxide in said (iv), 0-50 mol is preferable with respect to 1 mol of compounds of said (iv), and 0-20 mol is more preferable.

As said non-crosslinkable monomer (E-2), a C2-C20 monomer is preferable. More preferably, it is a C2-C15 monomer, More preferably, it is a C2-C10 monomer. In addition, when a non-crosslinkable monomer (E-2) is an alkylene oxide adduct, it is preferable that carbon number of structural parts other than an alkylene oxide structural part is these values.

In the crosslinked polymer (I), the proportion of the structural unit (a) is preferably 50 to 100% by mass with respect to 100% by mass of all the structural units. More preferably, it is 70-100 mass%, More preferably, it is 80-100 mass%, Most preferably, it is 90-100 mass%.

In the crosslinked polymer (I), the proportion of the structural unit (e) is preferably 0 to 50% by mass with respect to 100% by mass of all the structural units. More preferably, it is 0-30 mass%, More preferably, it is 0-20 mass%, Most preferably, it is 0-10 mass%.
When the crosslinked polymer (I) has a crosslinked structure derived from the crosslinkable monomer (E-1), the proportion of the structural unit (e-1) is the same as that of the structural unit (a) and the non-crosslinkable single molecule. It is preferable that it is 0.001-10 mass% with respect to a total of 100 mass% with the structural unit (e-2) derived from a monomer (E-2). More preferably, it is 0.01-5 mass%, More preferably, it is 0.05-3 mass%, Most preferably, it is 0.1-2 mass%.

When the cross-linked polymer (I) has a cross-linked structure derived from the cross-linkable monomer (E-1), the proportion of the structural unit (e-1) is such that the structural unit (a) and the structural unit (e It is preferable that it is 0.005-5 mol% with respect to a total of 100 mol% with -2. More preferably, it is 0.01-5 mol%, More preferably, it is 0.01-1 mol%, Most preferably, it is 0.05-0.8 mol%.

(Polymer (II))
The polymer composite composition of the present invention contains a polymer (II) other than the crosslinked polymer (I).
The polymer (II) is not particularly limited as long as it is other than the crosslinked polymer (I), but the glass transition temperature (Tg) is preferably 20 ° C. or higher. If the Tg of the polymer (II) is 20 ° C. or higher, the polymer (II) is entangled with the cross-linked polymer (I), so that the toughness of the cross-linked polymer (I) becomes smaller and is easily pulverized. Will be improved. More preferably, Tg is 20-700 degreeC, More preferably, it is 30-600 degreeC, Most preferably, it is 40-500 degreeC.

The polymer (II) may be different from the cross-linked polymer (I), but the unsaturated monomer (A) having a lactam structure, the unsaturated carboxylic acid monomer (B), an amine It is preferable to have a structural unit derived from at least one selected from the group consisting of the system monomers (C).
The unsaturated carboxylic acid monomer (B) is not particularly limited, but (i) unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, and salts thereof; ) Unsaturated dicarboxylic acids such as fumaric acid, maleic acid, methylene glutaric acid and itaconic acid, and salts thereof (which may be mono- or di-salts).
More preferred are acrylates and methacrylates.

The amine monomer (C) is not particularly limited as long as it has an amine structure, but is an alkyleneimine such as ethyleneimine; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( A quaternizing agent is added to N, N-dialkylamino group-containing (meth) acrylates such as (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, and the above monomers. Added monomers or neutralized products thereof with acids such as hydrochloric acid; N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide N, N-diethylaminopropyl (meth) acrylami N, N-dialkylamino group-containing (meth) acrylamides and the like, monomers obtained by adding a quaternizing agent to the above monomers, or neutralized products thereof by acid such as hydrochloric acid; monomethylaminoethyl (meth) acrylate, monoethyl Monomethylamino group-containing (meth) acrylates such as aminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate and the like, and neutralized products thereof by acid such as hydrochloric acid; monomethylaminoethyl Monoalkylamino group-containing (meth) acrylamides such as (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide, and hydrochloric acid thereof Neutralized product by acid; ester of (meth) acrylic acid and alkanolamine such as (meth) acrylic acid-2-aminoethyl and the like, and neutralized product by acid such as hydrochloric acid; N, N-diallylmethylamine and Monomers added with a quaternizing agent or neutralized products thereof with acids such as hydrochloric acid; neutralized products with allylamine and acids such as hydrochloric acid; vinylimidazoles and their salts or quaternized products thereof An unsaturated amine etc. are mentioned.
The amine monomer (C) is preferably an alkyleneimine such as ethyleneimine; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl ( N, N-dialkylamino group-containing (meth) acrylates such as (meth) acrylate and N, N-diethylaminopropyl (meth) acrylate, and monomers obtained by adding a quaternizing agent to the above monomers or acids such as hydrochloric acid. Neutralized products: unsaturated amines such as vinylimidazole and salts thereof or quaternized products thereof, more preferably ethyleneimine, N, N-dimethylaminoethyl (meth) acrylate; vinylimidazole.

When the polymer (II) has a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure, the proportion of the structural unit (a) in the polymer (II) is 100 masses of all structural units. It is preferable that it is 30-100 mass% with respect to%. More preferably, it is 50-100 mass%, More preferably, it is 70-100 mass%, More preferably, it is 90-100 mass%, Most preferably, it is 100 mass%.

When the polymer (II) has a structural unit (c) derived from the amine monomer (C), the proportion of the structural unit (c) in the polymer (II) is 100% by mass of the total structural units. 30 to 100% by mass is preferable. More preferably, it is 50-100 mass%, More preferably, it is 70-100 mass%.

The polymer (II) preferably has a structural unit (b) derived from the unsaturated carboxylic acid monomer (B). When it has the said structural unit (b), coloring of the polymer composite composition of this invention can be suppressed more fully.

When the polymer (II) has the structural unit (b), the proportion of the structural unit (b) in the polymer (II) is 50 to 100% by mass with respect to 100% by mass of all the structural units. preferable. More preferably, it is 70-100 mass%, More preferably, it is 90-100 mass%, Most preferably, it is 100 mass%.

The polymer (II) is an unsaturated monomer (A) having a lactam structure, an unsaturated carboxylic acid monomer (B), and other monomers (D) other than the amine monomer (C). ) -Derived structural unit (d).
The other monomer (D) is not particularly limited, and examples thereof include vinyl aryl monomers such as styrene, indene and vinylaniline; vinyl carboxylates such as vinyl acetate and vinyl propionate.

In the polymer (II), the proportion of the structural unit (d) is preferably 0 to 10% by mass with respect to 100% by mass of all structural units. More preferably, it is 0-8 mass%, More preferably, it is 0-5 mass%, Most preferably, it is 0-3 mass%.

When the polymer (II) has the structural unit (a) derived from the unsaturated monomer (A) having a lactam structure, the K value is preferably 10 to 130. When the K value of the polymer (II) having the structural unit (a) is in the above preferred range, the polymer (II) is sufficiently entangled with the crosslinked polymer (I), and the ease of pulverization is further improved. More preferably, it is 15-120, More preferably, it is 20-100.
The K value of the polymer can be measured under the following conditions.
<Measurement method of K value (Fikenture method)>
When the K value was less than 20, the viscosity of a 5% (g / 100 ml) solution was measured, and when the K value was 20 or more, the viscosity of a 1% (g / 100 ml) solution was measured. The sample concentration was converted to dry matter. When the K value is 20 or more, 1.0 g of the sample is accurately measured, put into a 100 ml volumetric flask, add distilled water at room temperature, dissolve completely with shaking, add distilled water to make exactly 100 ml. did. This sample solution was allowed to stand for 30 minutes in a thermostatic chamber (25 ± 0.2 ° C.), and then measured using an Ubbelohde viscometer. Measure the time for the solution to flow between the two markings. Several measurements were taken and averaged. In order to measure the relative viscosity, distilled water was similarly measured. Two obtained flow times were corrected based on the Hagenbach-Couette correction.

In the above formula, Z is a relative viscosity (ηrel) of a solution having a concentration C, and C is a concentration (%: g / 100 ml).
The relative viscosity ηrel is obtained by the following equation.
ηrel = (solution flow time) ÷ (water flow time)

When the polymer (II) has the structural unit (b) derived from the unsaturated carboxylic acid monomer (B), the weight average molecular weight is preferably 1,000 to 1,000,000. When the weight average molecular weight of the polymer (II) having the structural unit (b) is in the above preferred range, the polymer (II) is sufficiently entangled with the crosslinked polymer (I), and the pulverization is further improved. . More preferably, it is 2000-500000, More preferably, it is 3000-300000, Most preferably, it is 4000-200000.
The weight average molecular weight of the polymer (II) can be measured by GPC (gel permeation chromatography) under the following conditions.
Device: HLC-8320GPC manufactured by Tosoh Corporation
Detector: RI
Column: Shodex Asahipak GF-310-HQ, manufactured by Showa Denko KK
GF-710-HQ, GF-1G 7B
Column temperature: 40 ° C
Flow rate: 0.5 ml / min
Calibration curve: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate aqueous solution

When the polymer (II) has the structural unit (c) derived from the amine monomer (C), the weight average molecular weight is preferably 200 to 150,000. When the weight average molecular weight of the polymer (II) having the structural unit (c) is within the above preferred range, the polymer (II) is sufficiently entangled with the crosslinked polymer (I), and the ease of being pulverized is further improved. More preferably, it is 300-100000, More preferably, it is 400-80000.
The weight average molecular weight of the polymer (II) can be measured by GPC (gel permeation chromatography) under the following conditions.
Measuring equipment: HLC-8320GPC manufactured by Tosoh Corporation
Detector: RI
Column: Three Asahipak Column GF-310, 510, 710 HQs connected in series and used by Shodex Guard column: Asahipak Column GF-7M HQ
Column temperature: 40 ° C
Flow rate: 0.5 mL / min
Standard substance for calibration curve: Shodex standard P-82 (pullulan) (Mw: 5,900 to 788,000)
Eluent: 0.2M MEA (monoethanolamine) aqueous solution pH adjusted to 5.1 (pH adjusted with acetic acid)
Measurement method: The measurement object is dissolved in an eluent so as to have a solid content of about 0.5% by mass, and the molecular weight is measured using an object filtered through a filter as a measurement sample.

The production of the polymer composite composition is not particularly limited, but can be produced by a method for producing a polymer composite composition described later.

The present invention is also a polymer material comprising a crosslinked polymer having a lactam structure, wherein the crosslinked polymer has a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure, The polymer material is also a polymer material having an average particle size of 700 μm or less measured by the following method.
[Measuring method]
10 g of a polymer material classified to 1-2 mm with a JIS standard sieve and dried in advance at 150 ° C. for 1 hour is placed in a crusher (Oster Blender 6878-042, manufactured by Osaka Chemical Co., Ltd.), and the scale is crushed for 3 minutes according to Mix. To do.
Combining JIS standard sieves in descending order of opening (1000, 850, 500, 250, 100 μm, saucer), putting the polymer material after pulverization into the uppermost sieve, Shake for 3 minutes by adjusting the vibration adjustment scale to 6 with M-2 (Miki Co., Ltd.). After measuring the mass of the cross-linked polymer remaining on each sieve, the size of each sieve mesh and the particles that could not pass through the sieve (particles remaining on the sieve and those remaining on the larger sieve) The mass ratio (residual percentage) R relative to the total of all the collected particles is plotted on a semilogarithmic graph (horizontal axis: particle diameter (logarithmic scale), vertical axis: residual percentage), and R = 50% particles The diameter is defined as the average particle diameter of the polymer material according to this measurement method.
The value of the average particle diameter measured by the above method is an index indicating the ease of pulverization of the polymer material. That is, the average particle size of 700 μm or less means that the polymer material is sufficiently pulverized.
The average particle diameter of the polymer material is more preferably 5 to 600 μm, and still more preferably 10 to 500 μm.

The crosslinked polymer only needs to have a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure, and other units other than the unsaturated monomer (A) having a lactam structure. You may have the structural unit (e) derived from a monomer (E).
Specific examples and preferred examples of the unsaturated monomer (A) and other monomer (E) having a lactam structure, and a preferred ratio of the structural unit (a) and the structural unit (e) in the crosslinked polymer are: As described for the crosslinked polymer (I).
The production of the polymer material is not particularly limited, but can be produced by a method for producing a polymer composite composition described later.

<Method for producing polymer composite composition>
The present invention is also a method for producing a polymer composite composition comprising a crosslinked polymer having a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure, wherein the production method comprises a lactam A step of polymerizing a monomer component containing an unsaturated monomer (A) having a structure in the presence of a polymer different from the cross-linked polymer, and the cross-linked polymer is different from the cross-linked polymer. It is also a method for producing a polymer composite composition including at least one of the steps of mixing with a polymer.
The present invention is also a polymer composite composition obtained by the above production method.

Specific examples and preferred examples of the monomer component in the method for producing a crosslinked polymer composite composition, and different polymers are as described in the crosslinked polymer (I) and the polymer (II). The content ratios of the monomers (A) and (E) with respect to 100% by mass of the monomer component are the same as the ratios of the structural units (a) and (e) with respect to 100% by mass of all the structural units described above.
Moreover, as a polymer different from the crosslinked polymer used in the polymerization step or the mixing step, a commercially available polymer may be used, and the monomer component described in the polymer (II) is polymerized. You may use what was manufactured.
The amount of the polymer used in the polymerization step is preferably 0.01 to 10% by mass with respect to 100% by mass of the monomer component that is a raw material of the crosslinked polymer. More preferably, it is 0.05-8 mass%, More preferably, it is 0.1-8 mass%, Most preferably, it is 0.5-5 mass%.

The method of charging the monomer component and the polymer into the reaction vessel in the polymerization step is not particularly limited, a method of initially charging the entire amount into the reaction vessel at an initial stage, the polymerization of the monomer component, and Either a method of charging the polymer into the water-absorbing gel after polymerization or a method of charging the powder after drying as an aqueous solution of the polymer may be used. Preferably, the entire amount is charged all at once into the reaction vessel.

The polymerization may be performed in the absence of a solvent, or a solvent may be used. The polymerization may be performed by various conventionally known methods such as bulk polymerization, solution polymerization, suspension polymerization, reverse phase suspension polymerization, emulsion polymerization, reverse phase emulsion polymerization, precipitation polymerization, or cast polymerization. A thin film polymerization method, a spray polymerization method, or the like can be employed. The stirring method for carrying out the polymerization reaction is not particularly limited, but when a gel-like cross-linked product is produced, a double-arm kneader is used as a stirring device, and the shear of the double-arm kneader is used. It is more preferable to stir while subdividing by force. The polymerization step can be performed batchwise or continuously.

In the polymerization step, polymerization of the monomer component containing N-vinyl lactam can be initiated by adding a polymerization initiator, irradiating UV, applying heat, or light in the presence of a photoinitiator. The method etc. which irradiate can be employ | adopted.

In the polymerization step, when a solvent is used, examples of the solvent include one or more selected from water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, diethylene glycol, and other alcohols. .

In performing the polymerization in the polymerization step, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include peroxides such as hydrogen peroxide and t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2′-azobis (2 -Methylpropionate), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride Salt, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2 , 2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate hydrate, , 2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate, Azo compounds such as 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]; benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroper Organic peroxides such as oxides; redox that generates radicals by combining oxidizing agents and reducing agents, such as ascorbic acid and hydrogen peroxide, sodium sulfoxylate and t-butyl hydroperoxide, persulfate and metal salts A mold initiator or the like is preferred. Of these polymerization initiators, hydrogen peroxide, persulfate, and azo compounds are preferable, and azo compounds are most preferable. Among them, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2 '-Azobis [2- (2-imidazolin-2-yl) propane] disulfate hydrate, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl) Butyronitrile) is more preferred. These polymerization initiators may be used alone or in the form of a mixture of two or more.

As the usage-amount of the said polymerization initiator, with respect to 1 mol of monomer usage-amount (total usage-amount of the unsaturated monomer (A) which has a lactam structure, and the other monomer (E) mentioned above). It is preferably 0.1 g or more and 10 g or less, more preferably 0.1 g or more and 7 g or less, and further preferably 0.1 g or more and 5 g or less.
By making the usage-amount of an initiator into such a ratio, the ratio of the unreacted monomer contained in the polymer obtained can be fully reduced.

In the polymerization step, as a suitable dispersant when employing the reverse phase suspension polymerization method, specifically, for example, sorbitan fatty acid ester, sucrose fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, ethyl cellulose, Examples thereof include cellulose esters such as cellulose acetate, cellulose ethers, and carboxyl group-containing polymers such as α-olefin-maleic anhydride copolymers. These dispersants may be used alone or in combination of two or more. In addition, the hydrophobic organic solvent provided when employing the reverse phase suspension polymerization method is not particularly limited.

In the polymerization step, the polymerization temperature is not particularly limited, but a relatively low temperature is preferable because the molecular weight of the crosslinked product is increased, and the polymerization rate is further improved within the range of 20 ° C to 100 ° C. preferable. The reaction time may be appropriately set according to the reaction temperature, the type (property) and combination of the monomer component, the polymerization initiator, and the solvent, the amount used, etc. so that the polymerization reaction is completed. Good.

The material of the reaction vessel for performing the polymerization step is not particularly limited as long as the polymerization step can be performed, but it is preferable to use a reaction vessel of a material such as stainless steel. By conducting a polymerization reaction using a reaction vessel made of a material that easily transmits heat, the polymerization reaction proceeds sufficiently, and an unreacted monomer (unsaturated monomer having a lactam structure) contained in the resulting polymer. The content of the body etc.) can be reduced.
It is also preferable to use a reaction vessel made of a material such as polypropylene that does not elute iron. By using a reaction vessel made of these materials, the content of iron contained in the resulting polymer can be reduced.

The cross-linked polymer used in the step of mixing the cross-linked polymer and the polymer different from the cross-linked polymer is particularly as long as it has a structural unit (a) derived from the unsaturated monomer (A) having a lactam structure. The monomer component containing the unsaturated monomer (A) having a lactam structure is polymerized in the same manner as in the above-described polymerization step, except that the polymerization is not limited and polymerization is performed in the presence of a polymer different from the crosslinked polymer. Can be manufactured.

The amount of the polymer different from the crosslinked polymer used in the mixing step is preferably 0.01 to 10% by mass with respect to 100% by mass of the crosslinked polymer. More preferably, it is 0.05-8 mass%, More preferably, it is 0.1-8 mass%, Most preferably, it is 0.5-5 mass%.

The mixing method of the cross-linked polymer and the polymer different from the cross-linked polymer in the mixing step is not particularly limited, and the cross-linked polymer and the polymer different from the cross-linked polymer can be solidified without using a solvent. They can be mixed together. Alternatively, a crosslinked polymer and a polymer different from the crosslinked polymer may be mixed in a solvent, that is, the crosslinked polymer may be impregnated with a polymer solution different from the crosslinked polymer. A preferred mixing method is to impregnate a crosslinked polymer with a polymer solution.
When a cross-linked polymer and a polymer different from the cross-linked polymer are mixed with each other without using a solvent, the soluble content of the polymer composite composition tends to increase. Here, the soluble content of the polymer composite composition is a value measured by the method described in Examples.
The impregnation time for impregnating the crosslinked polymer with the polymer solution is not particularly limited, but is preferably 0.1 to 3 hours.

The method for producing a polymer composite composition of the present invention includes at least one of the polymerization step and the mixing step, but preferably includes the polymerization step because the soluble component is reduced.

The polymer composite composition may be produced by including an optional step in addition to the polymerization step or the mixing step. For example, a drying step, a pulverizing step, a classification step, a granulation step, a post-crosslinking step, and the like may be included.

The polymer composite composition is preferably produced including a drying step.
In particular, when the polymer composite composition is obtained by polymerization using a solvent and is in a gel state, that is, a gel-like polymer composite composition containing a solvent, the gel-like polymer composite It is preferable to provide a step of drying the composition. In the present invention, drying refers to an operation of increasing the solid content, and usually the ratio of the solid content to the weight of the entire polymer may be increased as compared with that before drying, but preferably the weight of the entire polymer is 100. The solid content is increased to 95% by mass or more, more preferably 96% by mass or more with respect to mass%. In addition, it is preferable that the upper limit of solid content is about 99 mass%. Drying may be performed at the same time as polymerization, and drying during polymerization and drying after polymerization may be used in combination, but more preferably, a drying step of drying using a drying apparatus after polymerization is provided. Here, the solid content of the polymer is a value measured by the following method.
About 1 g of polymer is weighed (mass W2 (g)) in a weighing can (mass W1 (g)) having a bottom diameter of about 5 cm, and left to stand in a constant temperature dryer at 150 ° C. for 1 hour to dry. . Weighing can after drying + mass of polymer (W3 (g)) is measured, and solid content is obtained from the following formula.
Solid content (mass%) = ((W3 (g) −W1 (g)) / W2 (g)) × 100

The drying step is preferably performed in the range of 80 ° C. to 250 ° C. through 50% or more of the entire time of the drying step, more preferably through substantially all the drying steps. By being in the above range, various physical properties of the polymer tend to be further improved.
The drying temperature is defined by the heat medium temperature, but if it cannot be defined by the heat medium temperature such as microwave, it is defined by the material temperature. The drying method is not particularly limited as long as the drying temperature is within the above range, and hot air drying, airless drying, reduced pressure drying, infrared drying, microwave drying and the like can be suitably used. Among these, it is more preferable to use hot air drying. The amount of drying air when hot air drying is used is preferably 0.01 to 10 m / sec, more preferably 0.1 to 5 m / sec. The range of the drying temperature is more preferably 110 ° C to 220 ° C, and further preferably 120 ° C to 200 ° C. The drying may be performed at a constant temperature or may be performed by changing the temperature. However, it is preferable that substantially all the drying steps are performed within the above temperature range.

The pulverization step is preferably performed using a pulverizer. When the production method of the present invention includes a drying step, pulverization may be performed before, during or after drying, but preferably after drying. The pulverizer is not particularly limited. For example, a roll pulverizer such as a roll mill, a hammer pulverizer such as a hammer mill, an impact pulverizer, a cutter mill, a turbo grinder, a ball mill, a flash mill, and a jet. A mill or the like is used. Among these, it is more preferable to use a roll mill in order to control the particle size distribution. In order to control the particle size distribution, it is more preferable to pulverize continuously twice or more, and it is more preferable to pulverize continuously three times or more.
Moreover, when grind | pulverizing twice or more, each grinder may be the same or different. It is also possible to use different types of pulverizers in combination.
Moreover, when pulverizing the polymer composite composition of the present invention to an average particle size of 100 μm or less, it is preferable to use a jet mill.
The temperature of the pulverization step is not particularly limited, but is preferably performed at 10 to 120 ° C. Since the crosslinked polymer obtained by the production method of the present invention has suitable toughness, it can be sufficiently pulverized without freezing. More preferably, it is 15-80 degreeC as temperature of a grinding | pulverization process.

For example, in order to control the crosslinked polymer to a specific particle size distribution, a classification step or a granulation step may be provided. For the classification, a sieve with a specific opening may be used. The classifier used for classification with a sieve is not particularly limited. For example, a vibration sieve (unbalance weight drive type, resonance type, vibration motor type, electromagnetic type, circular vibration type, etc.), in-plane motion sieve (Horizontal motion type, horizontal circle-linear motion type, three-dimensional circular motion type, etc.), movable screen type screen, forced stirring screen, screen vibration screen, wind screen, sonic screen, etc. are used, preferably vibration screen An in-plane motion sieve is used.

When the crosslinked polymer has a crosslinked structure formed by the above (2) to (5), in the method for producing the crosslinked body, the crosslinked structure is obtained after performing a polymerization step for polymerizing the monomer component. A post-crosslinking step is performed to form.
Examples of the method of post-crosslinking in the post-crosslinking step (crosslinking after polymerization) include, for example, (i) a method of irradiating the polymer obtained in the polymerization step with UV, γ rays, and electron beams, and (ii) in the polymerization step. A method of adding a reaction accelerator such as a condensing agent to self-crosslink the obtained polymer, (iii) a method of applying heat to the polymer obtained in the polymerization step, and (iv) a method of obtaining in the polymerization step. A method of adding a radical generator to the obtained polymer and then applying heat to self-crosslink, (v) a radical-polymerizable cross-linking agent (cross-linkable monomer) and radical polymerization to the polymer obtained in the polymerization step. Examples of the method include heating and / or light irradiation after the initiator is contained.
In addition, as a polymer used for a post-crosslinking process, what was manufactured from the monomer component may be used and a commercially available polymer may be used.

When the cross-linked polymer has a cross-linked structure formed by (2) above, the amount of the cross-linking agent used is 100 moles of reactive functional groups (reactive functional groups that react with the cross-linking agent) of the polymer. % Is preferably an amount such that the functional group of the crosslinking agent is 30 to 100 mol%. More preferably, it is 50-100 mol%. By using a crosslinking agent at such a ratio, a sufficient crosslinked structure can be formed, and the amount of unreacted crosslinking agent remaining in the resulting crosslinked product can be reduced.

Examples of the reaction accelerator used in the method (ii) include acids such as sulfuric acid and phosphoric acid; bases such as sodium hydroxide and potassium hydroxide; condensing agents such as N, N′-dicyclohexylcarbodiimide and the like. More than seeds can be used.
As the radical generator used in the method (iv), the same polymerization initiator as that used in the polymerization step described above can be used. Among the polymerization initiators, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxypivalate, octanoyl peroxide, succinic peroxide, t-hexylperoxy-2-ethylhexanoate, t- Peroxides such as butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, and t-butyl peroxymaleic acid are preferred.

When the cross-linked polymer has a cross-linked structure formed by (5) above, the amount of the cross-linkable monomer used in the post-crosslinking is 100% by mass of the polymer before the post-crosslinking step. On the other hand, it is preferable that it is 0.1-50 mass%. More preferably, it is 1-30 mass%. By using a crosslinkable monomer at such a ratio, a sufficient crosslinked structure can be formed, and the amount of unreacted crosslinkable monomer remaining in the resulting crosslinked product can be reduced. it can.

The polymer composite composition and the polymer material of the present invention are a surfactant, a volatile component, an aroma component, a deodorant component, an agrochemical component, a liquid fertilizer component, a cosmetic component, and the like, a moisturizer and a thickener in cosmetic applications. And preferably used as a dispersant or the like.
Although it does not restrict | limit especially as said cosmetics, For example, cosmetics for finishing, such as makeup foundations, foundations, and lipsticks; cosmetics for skin such as lotion, milky lotion, sunscreen, facial cleansers; cosmetics for hair such as champulins .
The polymer composite composition and the polymer material of the present invention are preferably used as a surfactant carrier. The present invention is also a surfactant carrier containing the polymer composite composition and / or polymer material of the present invention.

The surfactant-carrying agent of the present invention contains the polymer composite composition and / or polymer material of the present invention, for example, 10% by mass to 100% by mass with respect to 100% by mass of the surfactant-carrying agent. Also good. Preferably, it is 50 mass% or more and 99.8 mass% or less.

Surfactants that can be carried by the surfactant carrier of the present invention are nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants, and reactive agents. Although surfactant etc. are mentioned, it does not specifically limit. The surfactant-supporting agent of the present invention is particularly preferably used for supporting an anionic surfactant among the above-mentioned surfactants.

Examples of the anionic surfactant include alkylbenzene sulfonic acid (salt), alkyl sulfate, polyoxyethylene alkyl sulfate, alkane sulfonic acid (salt), polyoxyethylene alkyl ether methyl carboxylic acid (salt), linoleic acid, Examples include higher fatty acids such as oleic acid and salts thereof.

Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides such as glycerol monolaurate, polyoxyethylene-polyoxypropylene, and the like. Examples thereof include copolymers.

Examples of amphoteric surfactants include N-acylamidopropyl-N, N-dimethylammoniobetaine, N-acylamidopropyl-N ′, N′-dimethyl-N′-β-hydroxypropylammoniosulfobetaine, and the like. And examples of the cationic surfactant include monoalkyltrimethylammonium methosulfate and cationized cellulose.

The surfactant-carrying agent of the present invention may carry the above-mentioned surfactant alone or may carry two or more kinds.

The polymer composite composition and / or polymer material of the present invention has the above-described configuration and can be suitably used for cosmetics and the like because it is easily pulverized while maintaining liquid absorbency.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Measurement conditions of weight average molecular weight>
The weight average molecular weight of the polymer was measured using GPC (gel permeation chromatography) under the following conditions.

<Evaluation method of water absorption capacity>
About 0.1 g of the crosslinked polymer was accurately weighed (mass W5 (g)), placed in a 4 cm × 5 cm non-woven tea bag, and sealed by heat sealing. The tea bag was immersed in water at room temperature. After 24 hours, the tea bag was pulled up, placed on a Kim towel (manufactured by Nippon Paper Crecia Co., Ltd.) and drained for 10 seconds, and then the mass (W6 (g)) of the tea bag was measured. Separately, the same operation was performed without using a crosslinked polymer, and the mass (W4 (g)) of the tea bag at that time was determined as a blank. The liquid absorption capacity calculated according to the following equation was defined as the water absorption capacity.
Liquid absorption ratio (g / g) = (W6 (g) -W4 (g)) / W5 (g)

<Evaluation method of surfactant absorbent capacity>
About 0.1 g of the crosslinked polymer was accurately weighed (mass W8 (g)), placed in a 4 cm × 5 cm non-woven tea bag, and sealed by heat sealing. This tea bag was immersed in linoleic acid as a surfactant and then placed in a dryer at 40 ° C. After 24 hours, it was taken out from the dryer and allowed to cool for 10 minutes. Then, the tea bag was pulled up, placed on a Kim Towel (manufactured by Nippon Paper Crecia Co., Ltd.), drained for 10 seconds, and then the mass of the tea bag (W9 (g )) Was measured. Separately, the same operation was performed without using a cross-linked polymer, and the mass (W7 (g)) of the tea bag at that time was determined as a blank. The liquid absorption capacity calculated according to the following formula was defined as the surfactant liquid absorption capacity.
Liquid absorption ratio (g / g) = (W9 (g) -W7 (g)) / W8 (g)

<Measuring method of average particle diameter (easiness of pulverization) of polymer material>
10 g of a crosslinked polymer classified to 1-2 mm with a JIS standard sieve and dried in advance at 150 ° C. for 1 hour is placed in a pulverizer (Oster Blender 6878-042 type, manufactured by Osaka Chemical Co., Ltd.), and the scale is pulverized for 3 minutes according to Mix. did.
Combining JIS standard sieves from top to bottom (1000, 850, 500, 250, 100 μm, saucer), placing the above-mentioned crushed crosslinked polymer in the uppermost sieve, The vibration adjustment scale was adjusted to 6 with an instrument M-2, and shaken for 3 minutes. After measuring the mass of the cross-linked polymer remaining on each sieve, the size of each sieve mesh and the particles that could not pass through the sieve (particles remaining on the sieve and those remaining on the larger sieve) The mass ratio (residual percentage) R relative to the total of all the collected particles is plotted on a semilogarithmic graph (horizontal axis: particle diameter (logarithmic scale), vertical axis: residual percentage), and R = 50% particles The diameter was determined as the average particle diameter of the polymer material according to this measurement method, and used as an index of ease of pulverization.

<Method for Measuring Soluble Content of Polymer Composite Composition>
In a 110 ml glass screw tube, about 1 g (mass W10 (g)) of a crosslinked polymer and about 100 g (mass W11 (g)) of deionized water were accurately weighed and sealed. Then, after stirring for 16 hours or more using a magnetic stirrer at room temperature (rotation speed: 600 rpm), the mixture was filtered with a qualitative filter paper (model number: No. 2 manufactured by Advantech) to obtain a soluble component extract.
Next, weigh out about 10 g of the above extract (mass W13 (g)) into an aluminum cup (mass W12 (g)) having a bottom diameter of about 5 cm, and leave it in a constant temperature dryer at 120 ° C. for 2 hours. And dried. The mass (W14 (g)) of the dried aluminum cup + soluble component was measured, and the soluble content was determined from the following formula.
Soluble content (mass%) = ((W14 (g) −W12 (g)) / (W13 (g) × W10 (g) / W11 (g))) × 100

<Example 1>
40 parts of N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd.) (hereinafter also referred to as “VP”), 0.16 part of triallyl cyanurate (hereinafter also referred to as “CTA”) as a crosslinkable monomer (0 relative to VP) .18 mol%), sodium polyacrylate (manufactured by Nippon Shokubai Co., Ltd., product number: DL453, molecular weight (catalog value): 50000) (hereinafter also referred to as “PSA”) 0.57 parts (0.5 mass% based on VP) Then, 93.3 parts of deionized water was charged into a 250 ml polypropylene (hereinafter also referred to as “PP”) container. Next, stirring was started with a magnetic stirrer, and nitrogen substitution was performed at 100 ml / min for 30 minutes. Subsequently, it heated up to 45 degreeC, continuing stirring. After the liquid temperature was stabilized at 45 ° C., 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (hereinafter also referred to as “VA-044”) as a polymerization initiator was used. 0.90 parts of a 10% by mass aqueous solution (0.25 g with respect to 1 mol of the total amount of VP and CTA used) was added to initiate polymerization. After the polymerization reaction progressed and a gel was formed, aging was performed at 90 ° C. for 60 minutes to complete the polymerization. The obtained gel was cracked and decomposed 30 times with a table kneader (PNV-1H type manufactured by Chuo Rika Co., Ltd.) and dried at 120 ° C. for 2 hours to obtain a dried VP cross-linked polymer. Next, the obtained cross-linked polymer was pulverized with a pulverizer and then classified using a JIS standard sieve having a predetermined opening to obtain a particulate VP cross-linked polymer (1).
Next, with respect to the VP crosslinked polymer (1), the liquid absorption ratio of water and a surfactant (linoleic acid) and the ease of being pulverized were measured according to the measurement methods described above. Table 2 shows the various performances measured.

<Examples 2 to 6>
Particulate VP crosslinked polymers (2) to (6) were obtained in the same manner as in Example 1 except that PSA was charged as shown in Table 1.
Next, with respect to the VP cross-linked polymers (2) to (6), the water and surfactant absorption ratios and ease of pulverization (average particle diameter) were measured according to the measurement methods described above. Table 2 shows the various performances measured.

<Example 7>
A 250 ml PP container was charged with 50 parts of VP, 0.2 part of CTA as a crosslinkable monomer (0.18 mol% with respect to VP), and 117.1 parts of deionized water. Next, stirring was started with a magnetic stirrer, and nitrogen substitution was performed at 100 ml / min for 30 minutes. Subsequently, it heated up to 45 degreeC, continuing stirring. After the liquid temperature was stabilized at 45 ° C., 1.13 parts of a 10% by mass aqueous solution of VA-044 (0.25 g relative to 1 mol of the total amount of VP and CTA) was added as an initiator to initiate polymerization. did. After the polymerization reaction progressed and a gel was formed, aging was performed at 90 ° C. for 60 minutes to complete the polymerization. The obtained gel was cracked and decomposed 30 times with a table kneader (PNV-1H type manufactured by Chuo Rika Co., Ltd.) and dried at 120 ° C. for 2 hours to obtain a dried VP cross-linked polymer. To 10 parts of the obtained crosslinked polymer dried product, 25.0 parts of a solution obtained by further diluting PSA (manufactured by Nippon Shokubai Co., Ltd., product number: DL453 molecular weight (catalog value): 50000) with water (based on the dried VP crosslinked polymer) 2 mass% of PSA) was impregnated over 1 hour. The obtained gel was dried at 120 ° C. for 2 hours, pulverized with a pulverizer, and then classified using a JIS standard sieve having a predetermined opening to obtain a particulate VP crosslinked polymer (7).
Next, with respect to the VP cross-linked polymer (7), the water and surfactant absorption ratios and ease of pulverization were measured according to the measurement methods described above. Table 2 shows the various performances measured.

<Example 8>
In Example 7, the same procedure as in Example 7 was followed, except that 25.0 parts of a solution obtained by further diluting PSA with water was changed to 64.6 parts (PSA was 5% by mass with respect to the dried VP crosslinked polymer). A particulate VP crosslinked polymer (8) was obtained.
Next, with respect to the VP cross-linked polymer (8), the water absorption rate and the ease of pulverization of the surfactant and the surfactant were measured according to the measurement methods described above. Table 2 shows the measured performance.

<Example 9>
In Example 1, 0.57 parts of PSA (0.5% by mass with respect to VP) was added to polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., product number: K-30 K value (catalog value): 27.0 to 33.0) (below) A particulate VP crosslinked polymer (9) was obtained in the same manner as in Example 1 except that the content was changed to 2.0 parts (also referred to as “PVP”) (5 mass% with respect to VP).
Next, with respect to the VP cross-linked polymer (9), the water absorption rate of water and the surfactant and the ease of pulverization were measured according to the measurement methods described above. Table 2 shows the various performances measured.

<Example 10>
In Example 1, 0.57 part of PSA (0.5% by mass with respect to VP) was polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., product number: Epomin SP-200, molecular weight (catalog value): 10,000) (hereinafter also referred to as “PEI”). ) A particulate VP crosslinked polymer (10) was obtained in the same manner as in Example 1 except that the content was changed to 2.0 parts (5% by mass with respect to VP).
Next, with respect to the VP cross-linked polymer (10), the water absorption rate of water and the surfactant and the ease of pulverization were measured according to the measurement methods described above. Table 2 shows the various performances measured.

<Comparative Example 1>
A 250 ml PP container was charged with 50 parts of VP, 0.2 part of CTA as a crosslinkable monomer (0.18 mol% with respect to VP), and 117.1 parts of deionized water. Next, stirring was started with a magnetic stirrer, and nitrogen substitution was performed at 100 ml / min for 30 minutes. Subsequently, it heated up to 45 degreeC, continuing stirring. After the liquid temperature was stabilized at 45 ° C., 1.13 parts of a 10% by mass aqueous solution of VA-044 (0.25 g relative to 1 mol of the total amount of VP and CTA) was added as an initiator to initiate polymerization. did. After the polymerization reaction progressed and a gel was formed, aging was performed at 90 ° C. for 60 minutes to complete the polymerization. The obtained gel was cracked and decomposed 30 times with a table kneader (PNV-1H type manufactured by Chuo Rika Co., Ltd.) and dried at 120 ° C. for 2 hours to obtain a dried VP cross-linked polymer. Next, the obtained crosslinked polymer was pulverized by a pulverizer and then classified using a JIS standard sieve having a predetermined opening, to obtain a particulate comparative VP crosslinked polymer (1).
Next, with respect to the comparative VP cross-linked polymer (1), the water absorption rate and the pulverization ease of the surfactant were measured according to the measurement methods described above. Table 2 shows the various performances measured.

<Example 11>
The VP cross-linked polymer (3) obtained in Example 3 was pulverized until it passed through a JIS standard sieve having an opening of 250 μm to obtain a particulate VP cross-linked polymer (11).
When the VP cross-linked polymer (11) was measured with a dry particle size distribution measuring device (Microtrac MT3100II manufactured by Microtrac Bell Co., Ltd.), the cumulative 50% particle size (average particle size) was 94.70 μm. It was.

<Example 12>
The VP crosslinked polymer (3) obtained in Example 3 was pulverized until it passed through a JIS standard sieve having an opening of 38 μm to obtain a particulate VP crosslinked polymer (12).
When the average particle size of the VP crosslinked polymer (12) is measured with a dry particle size distribution measuring device (Microtrack MT3300EXII manufactured by Microtrack Bell Co., Ltd.), the cumulative 50% particle size (average particle size) is 22. .76 μm.

<Examples 13 to 16>
With respect to the VP crosslinked polymers (5) to (8) obtained in Examples 5 to 8, soluble components were measured by the above method. Table 3 shows the measurement results.

Claims (9)

A polymer composite composition comprising a crosslinked polymer having a lactam structure,
The polymer composite composition comprises a cross-linked polymer (I) having a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure, and a polymer different from the cross-linked polymer (I) ( II) and a polymer composite composition. The polymer composite composition according to claim 1, wherein the unsaturated monomer (A) having a lactam structure is an unsaturated monomer having a pyrrolidone ring. The polymer composite according to claim 1 or 2, wherein the crosslinked polymer (I) has a proportion of the structural unit (a) of 50 to 100% by mass with respect to 100% by mass of all structural units. Composition. The polymer composite composition according to any one of claims 1 to 3, wherein the polymer (II) has a glass transition temperature (Tg) of 20 ° C or higher. The polymer composite composition according to any one of claims 1 to 4, wherein the polymer (II) has a structural unit (b) derived from an unsaturated carboxylic acid monomer (B). 6. The polymer composite composition, wherein the content ratio of the polymer (II) is 0.01 to 10% by mass with respect to 100% by mass of the crosslinked polymer (I). The polymer composite composition according to any one of the above. A polymer material comprising a crosslinked polymer having a lactam structure,
The crosslinked polymer has a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure,
The polymer material has an average particle diameter of 700 μm or less measured by the following method.
[Measuring method]
10 g of a polymer material classified to 1-2 mm with a JIS standard sieve and dried in advance at 150 ° C. for 1 hour is placed in a crusher (Oster Blender 6878-042, manufactured by Osaka Chemical Co., Ltd.), and the scale is crushed for 3 minutes according to Mix. To do.
Combining JIS standard sieves in descending order of opening (1000, 850, 500, 250, 100 μm, saucer), putting the polymer material after pulverization into the uppermost sieve, Shake for 3 minutes by adjusting the vibration adjustment scale to 6 with M-2 (Miki Co., Ltd.). After measuring the mass of the cross-linked polymer remaining on each sieve, the size of each sieve mesh and the particles that could not pass through the sieve (particles remaining on the sieve and those remaining on the larger sieve) The mass ratio (residual percentage) R relative to the total of all the collected particles is plotted on a semilogarithmic graph (horizontal axis: particle diameter (logarithmic scale), vertical axis: residual percentage), and R = 50% particles The diameter is defined as the average particle diameter of the polymer material according to this measurement method. A method for producing a polymer composite composition comprising a crosslinked polymer having a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure,
The production method includes a step of polymerizing a monomer component containing an unsaturated monomer (A) having a lactam structure in the presence of a polymer different from the crosslinked polymer, and the crosslinked polymer and the A method for producing a polymer composite composition, comprising at least one of steps of mixing a polymer different from a crosslinked polymer. A polymer composite composition obtained by the production method according to claim 8.