JPH0657007A - Method for delustering resin - Google Patents

Abstract

PURPOSE:To obtain the resin (plastic and/or elastomer) having a delustered appearance and excellent moldability by adding a specific crosslinked polymer as a delustering agent to a resin. CONSTITUTION:(A) 100 pts.wt. of a resin (plastic and/or elastomer) and (B) 0.01-50 pts.wt. of a crosslinked polymer are mixed with each other to produce the resin having a delustered appearance. The crosslinked polymer is produced by copolymerizing B1: 99.6-99.999wt.% of a monomer component having a polymerizable unsaturated group in the molecule and containing a monomer [preferably an alkyl (meth)acrylate having a 3-30C aliphatic hydrocarbon group] having a solubility parameter (SP value) of 9 or lower as a main monomer preferably in an amount of 70wt.% or more with B2: 0.001-0.4wt.% (B1+B2=100%) of a crosslinking monomer having two or more of polymerizable unsaturated bonds in the molecule [e.g. ethylene glycol di(meth)acrylate] in the presence of a polymerization initiator.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin matting method. More specifically, it relates to a method of kneading a specific cross-linked polymer into a resin to provide a resin having a matte appearance and excellent moldability.

[0002]

2. Description of the Related Art Conventionally, polymer compounds such as plastics and elastomers, so-called resins, have excellent resin physical properties (processability, flexibility, glossiness, elasticity, brittleness, handleability, etc.), resin performance (stability, durability). , Flame retardancy, vibration control, heat retention, etc.)
It is used in various fields due to its processability (releasability, kneading property, etc.). However, car interiors, home appliances,
In the field of furniture and the like, non-reflectivity is required from the feeling of calmness and luxury, and the demand for resins whose surface gloss is suppressed is increasing.

As a method for suppressing the gloss of the resin surface, embossing of the mold surface, matte coating, compounding an inorganic material or a rubber component, and graft-copolymerizing a resin of another component for phase separation. There is a method to wake it up. But,
Sufficient results have not been obtained by the conventional methods. For example, in embossing the metal surface, it is difficult to control the mold and set the molding conditions, and the inorganic compound has a drawback that the specific gravity of the resin increases and the impact strength decreases. In addition, the rubber composition has drawbacks such as a decrease in rigidity and a non-uniform composition. Further, the graft copolymerization of the resin of the other component has an effect, but the cost is increased and there is a problem in versatility.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the conventional resin matting methods.

That is, an object of the present invention is to provide a resin having a matte appearance and excellent moldability by kneading a specific crosslinked polymer into the resin.

[0006]

[Means for Solving the Problems] The present inventors have provided a resin having a matte appearance and excellent moldability by containing a specific crosslinked polymer in the resin as a matting agent. They have found what they can do and have completed the present invention.

That is, in the present invention, a monomer (A) having a polymerizable unsaturated group in the molecule having a solubility parameter (SP value) of 9 or less as the main component (A) is 99.6.
-99.999% by weight and 0.001 of a crosslinkable monomer (B) having at least two polymerizable unsaturated groups in the molecule
To 0.4% by weight (however, the total amount of the monomers (A) and (B) is 100% by weight), the crosslinked polymer (I) obtained by polymerizing The present invention relates to a resin matting method, characterized in that the resin is contained in an amount of 0.01 to 50 parts by weight with respect to parts.

[0008]

The solubility parameter (SP value) is generally used as a measure of the polarity of a compound, and in the present invention, a value derived by substituting the Hoy cohesive energy constant into the Small calculation formula is applied, The unit is (cal /
represented by cm ^{3) 1/2.}

The monomer constituting the main component of the monomer (A) used in the present invention is a monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule. It is the body. When a monomer having a solubility parameter (SP value) of more than 9 is used as the main component of the monomer (A), a crosslinked polymer having a good kneadability with a resin cannot be obtained and the matting effect becomes nonuniform. Therefore, it is not preferable.

Examples of the monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule include, for example, methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth). Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate,
Dodecyl (meth) acrylate, isobornyl (meth)
Acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, octylphenyl (meth)
Acrylate, nonylphenyl (meth) acrylate,
Unsaturated carboxylic acid esters such as dinonylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, menthyl (meth) acrylate, dibutyl maleate, didodecyl maleate, dodecyl crotonate and didodecyl itaconate; (di) butyl ( (Meth) acrylamide, (di) dodecyl (meth) acrylamide,
(Meth) acrylamide having a hydrocarbon group such as (di) stearyl (meth) acrylamide, (di) butylphenyl (meth) acrylamide, (di) octylphenyl (meth) acrylamide; 1-hexene, 1-octene, isooctene, Α-Olefins such as 1-nonene, 1-decene, 1-dodecene; alicyclic vinyl compounds such as vinylcyclohexane; allyl ethers having a hydrocarbon group such as dodecyl allyl ether; vinyl caproate, vinyl laurate, palmitic acid Vinyl ester having a hydrocarbon group such as vinyl and vinyl stearate;
Vinyl ether having a hydrocarbon group such as butyl vinyl ether and dodecyl vinyl ether; aromatic vinyl compounds such as styrene, t-butyl styrene, octyl styrene, and the like, and one or more of these monomers can be used. You can

Among these, the monomer (A) which gives a more excellent matting effect to the resin has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms and is an alkyl (meth) acrylate. A main component of at least one unsaturated compound (a) selected from the group consisting of: alkyl aryl (meth) acrylate, alkyl (meth) acrylamide, alkyl aryl (meth) acrylamide, fatty acid vinyl ester, alkyl styrene and α-olefin. Are preferred.

Such solubility parameter (SP value)
Is 9 or less, the amount used in the monomer (A) is
The proportion is 50% by weight or more, more preferably 70% by weight or more, based on the total amount of the monomer (A). When the amount of the monomer having a solubility parameter (SP value) of 9 or less in the monomer (A) is less than 50% by weight, a crosslinked polymer having a good kneadability with a resin cannot be obtained, and a matting effect is obtained. It is not preferable because it causes unevenness.

Therefore, in the present invention, 50 monomers having a solubility parameter (SP value) of 9 or less are contained in the monomer (A).
It is necessary to contain at least 50% by weight, but the solubility parameter (SP value) is 50% by weight or less in the monomer (A).
May contain more than 9 monomers. Examples of such a monomer include (meth) acrylic acid, acrylonitrile, maleic anhydride, fumaric acid, hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. be able to.

Examples of the crosslinkable monomer (B) used in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, N, N'-methylenebis (meth) acrylamide, N, N'-propylenebis (meth) acrylamide, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, polyfunctional (meth) obtained by esterification of alkylene oxide adduct of polyhydric alcohol (eg glycerin, trimethylolpropane or tetramethylolmethane) with (meth) acrylic acid Examples thereof include acrylate and divinylbenzene, and one or more of these crosslinkable monomers can be used.

The proportions of the monomer (A) and the crosslinkable monomer (B) in the monomer component used for producing the crosslinked polymer (I) are the same as those of the monomer (A) and the crosslinkable monomer. The monomer (A) is 99.6 to 9 relative to the total amount of the monomer (B).
9.999 wt% range, the crosslinkable monomer (B) is 0.0
It is in the range of 01 to 0.4% by weight.

When the amount of the monomer (A) is 99.6% by weight or less and the amount of the crosslinkable monomer (B) exceeds 0.4% by weight, the crosslink density of the obtained crosslinked polymer becomes too high. It is not preferable because a crosslinked polymer having a good kneadability with the resin cannot be obtained and the matting effect becomes uneven. Further, the monomer (A) is 9
When it exceeds 9.999% by weight, the compatibility of the obtained crosslinked polymer with the resin is excessively increased, so that a sufficient matting effect cannot be obtained, which is not preferable.

To produce the crosslinked polymer (I), the above-mentioned monomer components may be copolymerized using a polymerization initiator. The copolymerization can be carried out by a known method such as suspension polymerization, bulk polymerization or emulsion polymerization.

In the suspension polymerization, for example, an emulsifier having a high HLB value or a protective colloid agent such as polyvinyl alcohol, hydroxyethyl cellulose or gelatin is used to suspend the monomer component in water to prepare an oil-soluble polymerization initiator. The polymerization may be carried out in the presence of Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, 2,2′-azobisisobutyronitrile, and 2,2′-azobisdimethylvaleronitrile. The azo compound can be used, and the polymerization temperature is preferably in the range of 0 to 150 ° C. The resulting aqueous suspension of fine particulate resin of about 10 to 1000 μm is filtered and dried to obtain the desired crosslinked polymer (I).

Bulk polymerization is carried out, for example, by pouring a monomer component into a mold in the presence of the above-mentioned polymerization initiator and polymerizing the mixture under conditions of 0 to 150 ° C. to obtain the desired crosslinked polymer (I).
Is obtained.

In emulsion polymerization, the monomer components are suspended in water using, for example, an anionic or nonionic emulsifier or a composite emulsifier thereof, and a persulfate such as ammonium persulfate or potassium persulfate or a water-soluble azo compound is suspended. It is possible to use it as a polymerization initiator and polymerize it together with a reducing agent, a pH adjusting agent, an antioxidant, an antistatic agent, etc., if necessary, and carry out the polymerization under the condition of 0 to 150 ° C. The desired crosslinked polymer (I) is obtained.

The resin matting method of the present invention is effective for all resins called plastics and / or elastomers. Examples of the resin that is the object of the matting method of the present invention include polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polystyrene, (meth) acrylic resin, polyvinyl alcohol, polyolefin, polyethylene terephthalate, polybutylene terephthalate, polyacetal, and polycarbonate. , Homopolymers and copolymers of polyamide, acetyl cellulose, fluororesin, phenolic resin, urea resin, melanin resin, polyester resin, allyl resin, silicone resin, epoxy resin, AS resin, ABS resin, synthetic rubber, natural rubber, etc. Or a mixture of those resins can be mentioned.

In the present invention, the resin may contain an additive for modifying the resin, if necessary. The resin modifying additive is not particularly limited as long as it is added for the purpose of resin modification, and examples thereof include a plasticizer, a softening agent, a softening aid, a flame retardant, a smoke suppressant, and an antistatic agent. , Stabilizers, anti-aging agents,
Copper damage inhibitor, metal deactivator, antioxidant, ozone deterioration inhibitor, ultraviolet absorber, light stabilizer, mastication accelerator, tackifier, lubricant, slip agent, internal release agent, colorant , Antifouling agent, antifouling agent, antifogging agent, antifungal agent, antiseptic agent, heat retaining agent, foaming agent, scorch inhibitor, antiseismic agent, impact resistance improver, solvent, termite repellent, repellent, fragrance Agents, surface treatment agents, wetting agents, surfactants, emulsifiers, destabilizers, slow coagulants, defoamers, foam suppressors, antifreeze agents, freeze-thaw stabilizers, creaming agents,
Examples thereof include a dispersant, a thickener, a coagulant, a heat sensitive agent, a foaming agent, a bubble stabilizer, a film-forming aid and a modifier for a sealing gasket.

Further, the resin modifying additive used in the present invention is not limited to the above-mentioned additives, but other additives used for the purpose of resin modifying such as "Handbook Rubber" issued by Rubber Digest Co. -Additives described in "Latest version of plastic compounding chemicals" (published in March 1989) and "New version plastic compounding agents-basic and applied-" issued by Taisei Co., Ltd.

To carry out the method of the present invention, the resin may contain the crosslinked polymer (I). The method of incorporating the crosslinked polymer (I) into the resin is not particularly limited, and may be added and mixed with the resin, or may be added and mixed with the resin modifying additive and then mixed with the resin. Further, the cross-linked polymer (I) may be added and mixed when the resin and the resin-modifying additive are mixed using a ribbon blender, a Banbury mixer, a Heisil mixer, or another compounding machine or mixer.
When the resin is molded by various molding machines, the cross-linked polymer (I) may be added and mixed at the time of premixing or molding.

In order to deluster the resin by the method of the present invention, it is preferable to disperse the crosslinked polymer (I) in the resin as uniformly as possible. When the resin and the crosslinked polymer (I) are mixed, the mixture is heated to the extent that the crosslinked polymer (I) or the resin is not decomposed or the resin modifying additive is not volatilized or deteriorated. It is also possible to achieve uniform dispersion of (I).

The mixing ratio of the crosslinked polymer (I) is such that the resin 10
The amount is 0.01 to 50 parts by weight with respect to 0 part by weight of the crosslinked polymer (I). When the amount of the crosslinked polymer (I) used is less than 0.01 part by weight, the matting effect is insufficient. Further, if the cross-linked polymer (I) is used in an amount of more than 50 parts by weight, the original properties of the resin are significantly changed, which is not preferable.

The resin delustered by the method of the present invention is molded by various molding methods, for example, and becomes a molded article having a resin-modifying effect and preferable surface properties maintained for a long period of time. As a molding method,
When the resin is a thermoplastic resin, for example, use an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calender molding method, a slush molding method, a dip molding method, a foam molding method, or the like. When the resin is heat, light, radiation and other curable resin, for example, compression molding method, transfer molding method, injection molding method, low pressure molding method, lamination molding method and the like can be adopted.

In the resin used in the present invention, if necessary, alumina, antimony trioxide, asbestos, barite, calcium carbonate, anhydrous gypsum, kaolin clay, carbon black, diatomaceous earth, feldspar powder, acid clay, quartz, Graphite, magnesium carbonate, magnesium hydroxide,
Magnesium oxide, mica, molybdenum disulfide, wax clay, sericite, fine silicic acid, silica side, slate powder, talc, titanium oxide, vermiculite, volcanic ash, whiting, precipitated calcium carbonate, ground calcium carbonate, hydrous silicic acid, Fillers such as anhydrous silicic acid, hydrous silicate, kaolin clay, hard clay, calcined clay, fine powder talc, glass yarn, roving, chopped strand, chopped strand mat, glass cloth,
A reinforcing agent such as glass tape, roving cloth and milled fiber may be contained.

Further, when the resin composition containing the crosslinked polymer (I) used in the method of the present invention is recovered after use, it can be repeatedly used in the present invention.

[0030]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the examples, parts and% are based on weight unless otherwise specified.

[0031]

Reference Example 1 A 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube and a reflux condenser was charged with 3 parts of gelatin and 3 parts of water.
It was dissolved in 100 parts and charged, the inside of the flask was replaced with nitrogen while stirring, and the mixture was heated to 40 ° C. under a nitrogen stream. Then, as the monomer (A), nonylphenyl acrylate (SP value:
8.3) 99.794 parts, 0.206 parts of 1,6-hexanediol diacrylate as a crosslinkable monomer (B), and benzoyl peroxide 0.5 as a polymerization initiator.
Part solution at once at 400 rpm
The mixture was vigorously stirred under the conditions of.

Then, the temperature in the flask was raised to 80 ° C. and maintained at the same temperature for 2 hours to carry out the polymerization reaction. Then, the temperature in the flask was further raised to 90 ° C. and maintained for 2 hours to complete the polymerization. Let After completion of the polymerization, the granular product was filtered off, washed with water and dried at 60 ° C. to give a particle size of 10
A crosslinked polymer (1) having a size of 0 to 1000 μm was obtained.

[0033]

Reference Example 2 In Reference Example 1, 61.111 parts of dodecyl acrylate (SP value: 7.9) as a monomer (A) and N, N-dioctylacrylamide (SP value: 8.
2) 38.515 parts, polypropylene glycol dimethacrylate (molecular weight 400 as crosslinkable monomer (B)
0) A crosslinked polymer (2) having a particle size of 100 to 1000 μm was obtained by the same method as in Reference Example 1 except that 0.371 part was used instead.

[0034]

Reference Example 3 Stearyl acrylate (SP value: 7.8) 99.855 as the monomer (A) in Reference Example 1
And a particle size of 100 to 1000 μm by the same method as in Reference Example 1 except that 0.145 parts of 1,4 butanediol diacrylate was used as the crosslinking monomer (B).
A cross-linked polymer (3) was obtained.

[0035]

Reference Example 4 Isobornyl acrylate (SP value: 8.4) 99.796 as the monomer (A) in Reference Example 1
Parts, a crosslinked polymer (4) having a particle size of 100 to 1000 μm was obtained by the same method as in Reference Example 1, except that 0.204 part of ethylene glycol diacrylate was used as the crosslinkable monomer (B) instead. It was

[0036]

[Reference Example 5] A glass casting mold for polymerization (having a size of 5 x 5 x 1 cm) equipped with a thermometer and a gas introduction tube,
Dodecyl acrylate as monomer (A) (SP value:
7.9) A mixed solution consisting of 99.823 parts, 0.177 parts of ethylene glycol diacrylate as a crosslinkable monomer (B), and 0.1 parts of 2,2′-azobisdimethylvaleronitrile as a polymerization initiator. Inject and under a nitrogen stream 60
Polymerization reaction was carried out by heating at 0 ° C for 2 hours, then heated to 80 ° C and maintained for 2 hours to complete the polymerization. After cooling, the gel-like material was peeled off from the mold to obtain a crosslinked polymer (5).

[0037]

Reference Example 6 Hexadecyl methacrylate (SP value: 7.8) 49.93 as the monomer (A) in Example 5.
0 part and N-octyl methacrylamide (SP value:
8.6) except that 49.930 parts and 0.140 parts of divinylbenzene as the crosslinkable monomer (B) are used instead.
A crosslinked polymer (6) was obtained in the same manner as in Reference Example 5.

[0038]

Reference Example 7 Cyclohexyl methacrylate (SP value: 8.3) 99.7 as the monomer (A) in Reference Example 5
A crosslinked polymer (7) was obtained in the same manner as in Reference Example 5 except that 71 parts and 0.229 parts of N, N ′ methylenebisacrylamide as the crosslinkable monomer (B) were used instead.

[0039]

Reference Example 8 Isobornyl acrylate (SP value: 8.4) 99.796 as the monomer (A) in Reference Example 5
A crosslinked polymer (8) was obtained in the same manner as in Reference Example 5, except that 0.204 part of ethylene glycol diacrylate was used as the crosslinkable monomer (B).

[0040]

[Reference Example 9] In a 500 ml flask equipped with a thermometer, a stirrer, a gas introduction tube, two dropping funnels and a reflux condenser,
Charge 3 parts of polyoxyethylene glycol (degree of polymerization 17) monononylphenyl ether and 100 parts of water, and
The inside of the flask was replaced with nitrogen while stirring under the condition of 00 rpm, and the flask was heated to 70 ° C. under a nitrogen stream.

On the other hand, t-butylstyrene (SP value: 7.9) 54.881 parts and 1-decene (SP value: 7.0) 44.903 parts as the monomer (A), a crosslinkable monomer As the monomer (B), a monomer composed of 0.216 parts of divinylbenzene was added to polyoxyethylene glycol (degree of polymerization 17).
In an aqueous solution prepared by dissolving 3 parts of monononylphenyl ether in 150 parts of water, a homogenizer was used for mixing for 10 minutes at 5000 rpm to prepare 253 parts of an aqueous dispersion of a monomer. Further, 1 part of sodium persulfate as a polymerization initiator was dissolved in 50 parts of water to prepare 51 parts of an aqueous solution of the polymerization initiator.

Each of the aqueous dispersion of the monomer and the aqueous solution of the polymerization initiator was placed in a separate dropping funnel, and 50 parts of the aqueous dispersion of the monomer and 5 parts of the aqueous solution of the polymerization initiator were placed in a flask. Polymerization started. Then, while maintaining the inside of the flask under a nitrogen stream at 70 ° C., the remaining aqueous dispersion of the monomer was dropped over 120 minutes, and at the same time, the remaining aqueous sodium persulfate solution was dropped over 240 minutes. After completion of the dropping, the temperature was maintained at 70 ° C. for 120 minutes to complete the polymerization to obtain an aqueous dispersion of the crosslinked polymer (9). The average particle diameter of the crosslinked polymer (9) was 0.2 μm, and the content of the crosslinked polymer (9) in the obtained aqueous dispersion was 25.5%.

[0043]

Reference Example 10 Nonylphenyl acrylate (SP value: 8.3) 74.7 as the monomer (A) in Reference Example 9
93 parts and hydroxyethyl acrylate (SP value:
10.3) 24.931 parts and a cross-linked polymer (using the same method as in Reference Example 9 except that 0.276 parts of 1,6-hexanediol diacrylate was used as the cross-linkable monomer (B) instead. An aqueous dispersion of 10) was obtained. The average particle size of the crosslinked polymer (10) was 0.15 μm, and the content of the crosslinked polymer (10) in the obtained aqueous dispersion was 25.0%.
Met.

[0044]

Reference Example 11 In Reference Example 9, 99.811 parts of vinyl laurate (SP value: 7.9) as the monomer (A) and 0.187 parts of trimethylolpropane triacrylate as the crosslinkable monomer (B). An aqueous dispersion of the crosslinked polymer (11) was obtained by the same method as in Reference Example 9 except that was used instead. The average particle size of this crosslinked polymer (11) was 0.1.
5 μm, and the crosslinked polymer (1
The content of 1) was 25.0%.

[0045]

Reference Example 12 In Reference Example 9, t as the monomer (A)
-Butyl acrylate (SP value: 8.7) 99.796
Parts, an aqueous dispersion of the crosslinked polymer (12) was prepared in the same manner as in Reference Example 9 except that 0.204 parts of polyethylene glycol diacrylate (molecular weight 500) was used as the crosslinkable monomer (B). Obtained. This crosslinked polymer (12)
Had an average particle diameter of 0.2 μm, and the content of the crosslinked polymer (12) in the obtained aqueous dispersion was 25.0%.

[0046]

Comparative Reference Example 1 A method similar to Reference Example 1 except that the amount of nonylphenyl acrylate was changed to 97.585 parts and the amount of 1,6 hexanediol diacrylate was changed to 2.415 parts. Thus, a comparative crosslinked polymer (1) was obtained.

[0047]

Comparative Reference Example 2 Instead of 99.794 parts of nonylphenyl acrylate in Reference Example 1, 39.713 parts of nonylphenyl acrylate and acrylonitrile (SP
Value 9.2) 59.570 parts of Comparative cross-linked polymer (2) was prepared in the same manner as in Reference Example 1, except that the amount of 1,6 hexanediol diacrylate was changed to 0.717.
Got

[0048]

Comparative Reference Example 3 A comparative polymer (3) was obtained in the same manner as in Reference Example 1 except that 1,6 hexanediol diacrylate was not used in Reference Example 1.

[0049]

COMPARATIVE REFERENCE EXAMPLE 4 Comparative Reference Example 5 was repeated except that the amount of dodecyl acrylate was changed to 97.919 parts and the amount of ethylene glycol diacrylate was changed to 2.081 parts. United (4)
Got

[0050]

Comparative Reference Example 5 Dodecyl acrylate 3 in place of 99.823 parts of dodecyl acrylate in Reference Example 5
9.854 parts and methacrylic acid (SP value: 10.1)
A comparative crosslinked polymer (5) was obtained in the same manner as in Reference Example 5 except that 59.780 parts were used and the amount of ethylene glycol diacrylate was changed to 0.366 part.

[0051]

Comparative Reference Example 6 A comparative polymer (6) was obtained in the same manner as in Reference Example 5 except that 1,6 hexanediol diacrylate was not used in Reference Example 5.

[0052]

[Comparative Reference Example 7] Reference Example 11 except that the amount of vinyl laurate was changed to 98.401 parts and divinylbenzene was 1.599 parts instead of 0.216 parts of trimethylolpropane triacrylate in Reference Example 11. An aqueous dispersion of the comparative crosslinked polymer (7) was obtained in the same manner as in (1).

[0053]

Comparative Reference Example 8 Instead of 99.811 parts of vinyl laurate in Reference Example 11, vinyl laurate 39.91 was used.
1 part and hydroxyethyl acrylate (SP value: 1
0.3) 59.867 parts were used, and divinylbenzene 0.2 was used instead of trimethylolpropane triacrylate.
An aqueous dispersion of comparative crosslinked polymer (8) was obtained in the same manner as in Reference Example 11 except that the amount was changed to 22 parts.

[0054]

Comparative Reference Example 9 An aqueous dispersion of Comparative Polymer (9) was obtained in the same manner as in Reference Example 11 except that trimethylolpropane triacrylate was not used in Reference Example 11.

[0055]

Example 1 Crosslinked polymer (1) obtained in Reference Examples 1 to 4
To (4) and 0.5 parts of the comparative polymers (1) to (3) obtained in Comparative Reference Examples 1 to 3, 100 parts of polyvinyl chloride having a polymerization degree of 1000, and 35 parts of di2-ethylhexyl phthalate. Epoxidized soybean oil 2 parts, Sn stabilizer (manufactured by Tokyo Fine Chemical Co., Ltd. EMBILIZER ™
F-2) 2 parts and 2 parts of polyethylene glycol monolaurate are mixed with a mixer, and a sheet-shaped resin molded product (1) to (4) having a thickness of 0.6 mm by a biaxial stretching roll at 150 ° C. and comparison. Molded into resin molded products (1) to (3). For comparison, a sheet-shaped blank resin molded article to which no crosslinked polymer or comparative polymer was added was molded. The matt state of these resin molded products was visually evaluated for light reflectance (reflectance of mirror surface of 60 degrees), and the results are shown in Table 1.
It was shown to.

[0056]

[Table 1]

[0057]

Example 2 Crosslinked polymer (5) obtained in Reference Examples 5-8
To (8) and Comparative Polymers (4) to (6) obtained in Comparative Reference Examples 4 to 6, 0.5 parts of each, 15 parts of chlorinated paraffin, 0.1 part of zinc stearate, a lubricant (Kao) By dipping in a mixture consisting of 1 part of Electrostriper H) manufactured by the same company and 10 parts of dioctyl sebacate for 24 hours, a slurry composition comprising a crosslinked polymer and a resin modifying additive was obtained. Each of these slurry compositions was mixed with 100 parts of polystyrene pellets, then roll kneaded at 175 ° C for 10 minutes and then at 175 ° C for 5 minutes.
Sheet-shaped resin molded products (5) to (8) and a comparative resin molded product (4) to which a thickness of 0.5 mm is obtained by pressing for minutes.
(6) was obtained. For comparison, a sheet-shaped blank resin molded article to which no crosslinked polymer or comparative polymer was added was molded. The matte state of these resin molded products was visually evaluated with respect to light reflectance (reflectance of mirror surface of 60 degrees), and the results are shown in Table 2.

[0058]

[Table 2]

[0059]

Example 3 Aqueous dispersions of crosslinked polymers (9) to (12) obtained in Reference Examples 9 to 12 and comparative polymers (7) to (9) obtained in Comparative Reference Examples 7 to 9 were prepared. 2 parts each, 100 parts polypropylene powder, 2,6-di-tert-butyl-
After mixing 0.5 part of 4-methylphenol, 0.5 part of calcium stearate, 10 parts of octyl azelate, 4 parts of tetrabromobisphenol A and 30 parts of calcium carbonate, extrusion molding was carried out at 260 ° C. by a T-die method,
Sheet-shaped resin molded product (9) with a thickness of 0.6 mm
(12) and comparative resin molded products (7) to (9) were obtained.
For comparison, a sheet-shaped blank resin molded article to which no crosslinked polymer or comparative polymer was added was molded. For these resin molded products, the matte state was measured for light reflectance (mirror surface 60).
Degree of reflectance) and visually evaluated, and the results are shown in Table 3.

[0060]

[Table 3]

[0061]

Example 4 Crosslinked polymer (1) obtained in Reference Examples 1 to 4
To (4) and 2 parts of each of the comparative polymers (1) to (3) obtained in Comparative Reference Examples 1 to 3, 100 parts of ABS resin,
Phenylenediamine stabilizer (Ouchi Shinko Chemical Industry Co., Ltd.)
Nocrac White) (1 part) was mixed with a Heisil mixer, and then extrusion molded by the T-die method to give a thickness of 0.6 mm.
Sheet-shaped resin molded products (1 ')-(4')
And comparative resin moldings (1 ')-(3') were obtained. For comparison, a sheet-shaped blank resin molded article to which no crosslinked polymer or comparative polymer was added was molded. The matt state of these resin molded products was visually evaluated with respect to light reflectance (reflectance at a mirror surface of 60 degrees), and the results are shown in Table 4.

[0062]

[Table 4]

[0063]

According to the resin matting method of the present invention, the resin can be effectively matted by kneading a small amount of the matting agent into the resin.

Further, the resin matting method of the present invention can simplify the conventional matting method, which has been complicated depending on the combination of a wide variety of additives and resins, and effectively works with a small amount of addition. Therefore, the physical properties of the resin are not impaired.

Therefore, according to the method of the present invention, it becomes possible to deluster a resin which could not be used due to a decrease in strength of the resin and an increase in cost.

Therefore, the present invention is effective as a matting method for all plastics and / or elastomers and can be used in a wide variety of fields.

Claims (1)

[Claims] 1. A monomer (A) having one polymerizable unsaturated group in the molecule whose main component is a monomer having a solubility parameter (SP value) of 9 or less 99.6 to 99.999 weight. % And 0.001 to 0.4% by weight of a crosslinkable monomer (B) having at least two polymerizable unsaturated groups in the molecule (however, the total amount of the monomers (A) and (B) is 100% by weight). %), And a cross-linked polymer (I) obtained by polymerizing a monomer component composed of 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin. Matting method.