JPH04142312A - Highly crosslinked flexible bead polymer - Google Patents

Abstract

PURPOSE:To provide a highly crosslinked flexible bead polymer excellent in flexibility, solvent resistance, heat resistance, etc., by copolymerizing a specified (meth)acrylic ester with a specified (poly)alkylene glycol in a specified weight ratio. CONSTITUTION:An ester (A) of acrylic acid with a 2-12C alcohol or methacrylic acid with a 6-12C alcohol is copolymerized with a (poly)alkylene glycol (B) of formula I or II (wherein X is H or CH3; R1 is OCH2CH2, OCH(CH3)CH2 or the like; and n is 1-14) in such amounts that the degree of crosslinking alpharepresented by formula III (wherein M1 is the molecular weight of component A; M2 is the molecular weight of component B; W1 is the number of grams of component A used; W2 is the number of grams of component B used; and n1 is the number of vinyl groups contained in one molecule of component A) is 0.01-0.4. In this way, a highly crosslinked flexible bead polymer having a modulus E', a glass transition temperature Tg and a particle diameter D which satisfy formulas IV, V and VI, respectively, can be produced.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a bead-shaped material suitable for use as a matting agent for paints, an anti-blocking agent, an additive for soft/wet touch paints, a modifier for plastics, etc. between polymers.

(Prior Art) The original purpose of paints has traditionally been three major items: rust prevention and imparting beauty to the object to be coated. However, today, with the diversification of needs, there is a demand for paints that provide new functionality and appeal to the senses of sight and touch.

In particular, a paint called "suede-like" has a soft, wet-touch texture and is attracting a lot of attention because it provides a strong coating with excellent scratch resistance and a matte, non-reflective finish. . This characteristic is obtained by adding and mixing fine spherical beads of soft polyurethane resin to the paint.

However, since soft polyurethane is used as a raw material, there are problems such as coloring due to heat, restrictions on outdoor use due to poor weather resistance, and restrictions on the range of application due to high cost. There is a need to develop soft, fine, spherical beads with the above characteristics using acrylic or other polymers. However, acrylic polymers have poor solvent resistance, and it is difficult to improve this. Although there are methods such as introducing crosslinking, the current goal is that softness is sacrificed and the desired result cannot be obtained.

(Problems to be Solved by the Invention) That is, an object of the present invention is to provide a coating material that is soft, heat resistant, abrasion resistant, impact resistant, chemical resistant, and suitable for obtaining a paint having visual and tactile functions. It is an object of the present invention to provide an industrially advantageous bead-shaped polymer having excellent weather resistance and durability.

(Means for solving the i! problem) The object of the present invention described above is (A) alcohol having 2 to 12 carbon atoms and acrylic acid, or acrylic acid having 6 to 12 carbon atoms;
The following esters of alcohol and methacrylic acid, (
B) Alkylene glycol or polyalkylene gelylcol represented by the following formula (a) or (b) (a) (b) (However, X is H or CH3, R is 0CH2C
H2, OCH(CH3) CH2, OCH(CH3) C
H2CH2t or 0-(CH2)6, and n represents an integer of 1 or more and 14 or less. ), the amounts of components (A) and (B) are adjusted so that the degree of crosslinking α is 0.0.
1 or more and 0° or less (W2/M2) X2 (Wl/Ml)X n 1+ (W2/M2)X 2
M1: Molecular weight of compound (A) M2: Molecular weight of compound (B) Wl: Weight (g) of compound (A) used in polymerization Wl: Weight (g) of compound (B) used in polymerization nl: Weight (g) of compound (B) used in polymerization A
) is used so that the number of vinyl groups in one molecule of ) is within the range of
This is achieved by a bead-shaped polymer characterized by having the physical properties of a) to (C).

(a) Elastic modulus (E゛) I X 1 0'≦ E' ≦ I X 1
0' (dyn/cm2) (b) Glass transition temperature (T g) -80≦Tg≦20 ('C) (c) Particle diameter (D) 0, 5≦D≦300 (μm>) Also, urethane paint In this case, it is necessary to improve the adhesion, and in addition to the above components (A) and (B), it is preferable to copolymerize a third component. In this case, (A) has 2 or more carbon atoms and 12 or less carbon atoms. An ester of an alcohol and acrylic acid, or an alcohol having 6 or more and 12 or less carbon atoms and methacrylic acid, (B) an alkylene glycol or polyalkylene glycol represented by the above formula (a) or (b), and (C ) Alcohol represented by the following general formula (c); CH2=C-Co-÷R2→-0H (c) (where x is H; l is cH3, mata, R2 has 2 to 3 carbon atoms (representing an alkylene group) as a main component, the amounts of component (A), component (C), and component (B) are determined such that the degree of crosslinking α is 0.01 or more and 0.4 or less W 2 / M2) × 2 α = (Wl/Ml) X n l+ (W2/M2
) X 2Ml: average molecular weight of compounds (A) and (C) expressed by the following formula;
AX+MCXWA+WCWA
+~vC MA: Molecular weight of compound (A) MC; Molecular weight of compound (C) WA: Weight of compound (A) used in polymerization (g) WC: Weight of compound (C) used in polymerization (g) M2 : Compound (B
) Molecular weight Wl: Amount (g) of compound (A) used in polymerization Wl: Weight (g) of degenerate compound (B) and (C) used in polymerization nl: One molecule of compound (A, ) used in polymerization The number of vinyl groups possessed is within the range of
This is achieved by a bead-shaped polymer characterized by having the physical properties of a) to (d).

(a) Elastic modulus (E') IX105≦E'≦IX10 @(dyn/ca
l'') (b) Glass transition temperature (Tg) -80≦Tg≦20 (℃) (c) Hydroxyl group density (qo+) 0.01≦qOH≦20 (m, eq/g) (d) Particle diameter (D ) 0, 6≦D≦300 (μm) The present invention will be explained in more detail below.

First, the bead-like polymer 〇 copolymer component according to the present invention will be explained in detail.

The component (A,) constituting the bead-like polymer of the present invention is an alcohol and alkyl acid having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, or an alcohol having 6 to 12 carbon atoms.
It is an ester of the following alcohol and methacrylic acid, and the alcohol constituting the ester has no equivalent limitation other than the number of carbon atoms. Examples of such ester include ethyl acrylate, butyl acrylate, , (meta)
Includes octyl acrylate, stearyl (meth)acrylate, etc. In the case of acrylic esters, esters of alcohol with less than 2 carbon atoms, and in the case of methacrylic acid, esters of alcohol with less than 6 carbon atoms lose softness, and when the number of carbon atoms exceeds 12, copolymerizability and polymerization rate decrease. The present invention cannot be achieved because of this. On the other hand, among the constituent components of the bead-like polymer of the present invention, the component (B) which acts as a crosslinking component is an alkylene glycol or polyalkylene gelicol represented by the above formula (i) or (b).

Examples of component (B) include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and hexamethylene glycol di(meth)acrylate.

alkylene glycol divinyl esters such as bis([(meth)acryloxyethoxy]phenyl)propane and tetraethylene glycol (meth)acrylate,
Tetraethylene glycol di(meth)acrylate, nonaethylene glycol (meth)acrylate, nonapropylene glycol di(meth)acrylate, bis([(
Examples thereof include polyalkylene glycol divinyl esters such as meth)acryloxyjetoxycophenyl)propane and bis([(meth)acryloxyφpolyethoxyquinone]phenyl)propane.

The ratio of component (A) to component (B) is such that the amount of component (A) and component (B) is such that the degree of crosslinking α is 0.01 or more and 0.01 or more. The range is preferably 4 or less, more preferably 0.05 to 0.
．． It is 25. Generally, as the proportion of component (B), which is a crosslinking component, increases, the crosslinking density increases and the solvent resistance improves, but on the contrary, the softness decreases. Specifically, if the degree of crosslinking α is less than 0.01, sufficient solvent resistance and heat resistance will not be exhibited and a tough coating film will not be obtained, while if it exceeds 0.4, sufficient softness will not be obtained. Therefore, the object of the present invention cannot be achieved.

Furthermore, in order to achieve the object of the present invention, softness is particularly important, but in terms of elastic modulus (Eo), I X 105≦E'≦I
cg+2). Note that Eo shown here has the following relationship with the complex dynamic elastic modulus (Eo): E°=E'+iE'' The real part of the complex dynamic elastic modulus is called the dynamic elastic modulus. If Eo exceeds lXl0e (dyn/cm2), the softness is insufficient, and lXl0
If it is less than 5 (dyn/cm2), the soft particles are sufficient, but the strength of the particles decreases and sufficient scratch resistance is not achieved, making it impossible to achieve the object of the present invention.

Further, in addition to the components (A) and (B), the component (C) which may be preferably added in some cases is an alcohol represented by the above general formula (c). , hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and the like.

Here, the ratio of component (A) and component (C) to component (B) is preferably used so that the degree of crosslinking α is in the range iii of 0.01 or more and 0°4 or less, and more preferably ,0.
It is necessary to set it in the range of 0.06 to 0.25. Furthermore, the objects of the present invention can be effectively achieved by using bead-like polymers in which the obtained particles have the following physical properties (a) to (d).

(a) Elastic modulus (Eo) I X 10S≦E' ≦I X 108 (dyn/c
m2) (b) Glass transition temperature (T g) -8057g≦20. ('C) (c) Hydroxyl group density (qos) 0.01≦qoH≦20 (meq/g) (d) Particle diameter (D) 0, 5≦D≦300 (μm) In this case, (c) The introduction of hydroxyl groups derived from the components improves adhesion to paints. The aforementioned hydroxyl group density (hereinafter referred to as qOH) is preferably in the range of 0.01 to 20 meQ/g, more preferably 0.5 to δme q/g, per dry weight of the particles. If it is larger than this range, sufficient softness will not be obtained due to the crosslinking effect and an increase in Tg, while if it is smaller than this range, sufficient adhesion may not be obtained depending on the type of paint and the scratch resistance may decrease. Therefore, both q and OH are calculated by reacting dry particles with acetic anhydride in a pyridine solvent, measuring the amount of acetic anhydride consumed by reacting with hydroxyl groups, or the change in weight of the gel. *1 gr of dry particles is 1
qOH when reacted with mmol of acetic anhydride is 1 m
eq/g.

It is also possible to replace a part of component (A) with other monomers exemplified below. In such cases, the amount of substitution with other monomers includes the replaced monomer (A)
It is determined by taking into consideration that if the Tg of the component copolymer is higher than room temperature, the sufficient luster of the invention will not be achieved. Other monomers that can be used to replace the above include, for example, vinyl halides and vinylidene halides; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; and salts thereof; (Meth)acrylic acid esters such as methyl acrylate, methoxyethyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate; hydroxyethyl (meth)acrylate, hydroxypropyl Hydroxy (meth)acrylates such as (meth)acrylate; Unsaturated ketones such as methyl vinyl ketone, phenyl vinyl ketone, and methyl isopropenyl ketone; Vinyl esters such as vinyl formate, vinyl acetate, and vinyl propionate; Methyl vinyl ether, Vinyl ethers such as ethyl vinyl ether and allyl glycidyl ether; acrylamide and its alkyl substituted products; unsaturated hydrocarbon sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, and p-styrene sulfonic acid; and their salts; styrene Styrene and its alkyl or halogen substituted products such as , α-methylstyrene and chlorostyrene; Allyl alcohol and its esters or ethers; Basic vinyl compounds such as vinylpyridine, vinylimidazole, and dimethylamine ethyl methacrylate; acrolein, Examples include vinyl compounds such as methacrolein, vinylidene cyanide, acrylonitrile, and methacrylonitrile.

As a method for producing the bead-shaped polymer of the present invention, various polymerization methods can be employed as long as the desired beads can be obtained, such as emulsion polymerization.

Examples include aqueous suspension polymerization. In aqueous suspension polymerization, for example, a predetermined monomer is added as a dispersion stabilizer to a system in which a specific water-soluble polymer is present, and an oil-soluble radical initiator is used.

In such a polymerization method, the water-soluble polymer to be present in the polymerization system is a monomer unit consisting essentially of an ethylenically unsaturated carboxylic acid or a salt thereof, and an ethylenically unsaturated sulfonic acid or a salt thereof. Water-soluble polymers containing monomeric units, or polyvinyl alcohol,
Examples include starch, polyvinylpyrrolidone, hydroxyalkyl cellulose, carboxyl alkyl cellulose, etc. In particular, monomer units consisting essentially of an ethylenically unsaturated carboxylic acid or its salt, and an ethylenically unsaturated sulfonic acid or its salt Good results are obtained when using a water-soluble polymer that binds monomer units to gold. and,
The amount added is 0.0% relative to the monomer. A range of 1 to 15% is recommended.

Further, examples of the oil-soluble radical polymerization initiator include the following azo compounds or organic peroxides. That is, as azo compounds, 2゜2'-azobisisobutyronitrile, 2,21-azobis(2-methyl-valeronitrile), 2,21-azobis(2,4-dimethylbutyronitrile), 2, 2″-azobis(2-methylcapronitrile), 2,2′-azobis(2°3.3-)dimethylbutyronitrile), 2,21-azobis(2,4,
4-1-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile>, 2.2'-azobis<2,4-dimethyl-4-ethoxyvaleronitrile), 2,2'- Azobis(2,4-dimethyl-4-n
-butoxyvaleronitrile), and examples of organic peroxides include acetyl peroxide, propionyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, and lauroyl peroxide.

3, 5. Diacyl peroxides such as 5-trimethylhexanoyl peroxide, benzoyl peroxide, diisopropyl baroxydicarbonate, di-2-ethylhexyl oxydicarbonate; t
Peroxy esters such as -butylperoxyisobutyrate, t-butylperoxybiparate, t-butylperoxyneodocaate, and t-butylperoxylaurate can be used. Of course, two or more of the above-mentioned oil-soluble radical polymerization initiators can also be used in appropriate combination.

Although it is difficult to define the amount of the initiator used, it is generally 0.2% to 2% based on the monomer weight.
．． It is used within the range of 0%.

In addition, regarding the pH of the polymerization system, if it is too alkaline or acidic, it will cause hydrolysis of the produced polymer regardless of the liquid type, so the pH should be between 2 and 9. Preferably 2
Set within the range of ~7.

Furthermore, the stirring conditions that play an important role in adjusting the particle size include the shape of the blades and the presence or absence of baffles.

It needs to be changed depending on the desired particle size, etc., and it is difficult to define it unambiguously, but the stirring speed is generally 50 to 2
It is recommended to set it in the range of 00Orpm. It should be noted that a seed shape or a turbine blade is suitable as the shape of the blade because it is easy to obtain a uniform particle size distribution.

Furthermore, the polymerization temperature is generally recommended to be 80°C or less, preferably in the range of 40 to 70°C, although it depends on the type of initiator.

Further, as the polymerization medium, it is desirable to use water from the viewpoint of industrial advantages, but there is no problem in coexisting with a water-miscible organic solvent or an electrolyte salt.

In this way, a wide range of polymeric beads can be suitably produced, generally from submicrons to several millimeters in size.

In addition, the polymer beads of the present invention are particularly heat resistant, weather resistant,
Due to its excellent solvent resistance and high softness, it is suitably used as an additive for paints with visual and tactile functions.
, preferably a particle size of 1 to 100 μm.

(Effects of the invention) In this way, the product has high softness and flexibility, excellent solvent resistance, excellent heat resistance and weather resistance, and strength that poses no problem in practical use. polymer beads,
A noteworthy effect of the present invention is that it can provide industrial advantages without requiring special equipment or complicated operations.

Since the polymer beads of the present invention have a high degree of softness, they can be used not only as additives for paints with visual and tactile functions, but also as antiblocking agents, lubricants, organic pigments9 diagnostic agents, and plastic modifiers. Used in various fields of application such as quality agents.

(Example) The present invention will be explained in more detail with reference to Examples below.
The scope of the present invention is not limited by the description of these Examples. Parts and percentages shown in the Examples indicate weight fractions unless otherwise specified.

In addition, the softness, solvent resistance, gloss and weather resistance of the beads are
It was measured by the method below.

(1) Softness of beads A cylinder with a radius of 9 mm and a height of approximately 1 mm was prepared using Rheo Spectra-DVE-V4 manufactured by Rheology Co., Ltd., and the elastic modulus of the particles was measured. Needless to say, the smaller this value is, the more excellent the softness is.

(2) After drying the solvent-resistant beads, Kijirol/Butanol/Cyclohexane/Butylcarpitol=40/15/15/
The sample was immersed in a mixed solvent of 30°C and stored at 50°C for 300 hours, after which the weight loss rate was measured. The smaller this value is, the better the solvent resistance is.

(3) After drying the heat-resistant beads, heat treatment was performed at 180° C. for 20 minutes, and the degree of coloring, fusion, and deformation of the particles was observed with the naked eye.

(4) Glass transition point 20℃/mi using a differential scanning calorimeter manufactured by Rigaku Denki Co., Ltd.
The dried beads were measured under the conditions of n to determine the glass transition point.

(5) Hydroxyl group density The hydroxyl group density was determined by reacting dry particles with acetic anhydride in a pyridine solvent, measuring the amount of acetic anhydride consumed by reacting with the hydroxyl groups, or the change in weight of the gel, and calculating from this. The qOH when 1 gr of dry particles is reacted with 1 mm01 of acetic anhydride is 1 meq/g.

(6) Gloss and Weather Resistance A test paint is prepared by uniformly dispersing beads in an amount equal to the solid content of the acrylic or urethane paint.

The paint was roll-coated onto ABS resin to a thickness of about 25 μm, and then baked to produce a coated board.

The gloss (%) of this coating film is measured by 60 degree specular reflectance. If the matte effect is high, the second value will be small.

For weather resistance, similar coated plates were prepared, and after 1000 hours of sunshine weather meter testing, the color difference ΔE was measured using a Color Analyzer Model 307 manufactured by Hitachi, Ltd., using the coated plate before the test as a standard plate. The smaller ΔE is, the better the weather resistance is.

(7) Regarding the tactile sensation, when the tester touches the coated board, a suede-like coated board with a soft, wet feel is marked as [0], and a coated board with a dry and rough feel is marked as [x].

(8) Scratch Resistance For scratch resistance, a coin scratch test was conducted, and those with no change were rated ``○'', and those with scratches that turned white or lost their luster were rated ``x''.

Example 1 Methacrylic acid/sodium P-styrene sulfonate = 70
/30 water-soluble polymer 6 parts and polyvinyl alcohol 3 parts
1 part was dissolved in 660 parts of water and charged into a polymerization tank equipped with a seed type stirrer. Next, 240 parts of ethyl acrylate and 60 parts of diethylene glycol dimethacrylate were added. 3 parts of 2-azobis(2,4-dimethylvaleronitrile) was dissolved and charged into the polymerization tank, and while stirring at 800 rpm,
When reacted at 60°C for 2 hours, the average particle size was 22 μm.
A true spherical bead-like polymer was obtained in a yield of 85%. The obtained beads were dried under closed conditions at 80° C. for 2 hours to form a dry powder.

Next, 50 parts of these beads were dispersed in 100 parts of an acrylic resin drying at room temperature; Acridic A-157 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) to prepare a paint. The paint,
After roll coating on ABS resin to a thickness of approximately 25 μm, 80
Baking treatment was performed at ℃ for 30 minutes to produce a coated board.

The evaluation results of the bead-shaped polymer of this invention are shown in Table 1.
Moreover, the evaluation results of the coating film produced using these beads are shown in Table 2.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that 170 parts of butyl acrylate was used instead of 240 parts of ethyl acrylate, and 130 parts of tetraethylene glycol dimethacrylate was used instead of 60 parts of diethylene glycol dimethacrylate. A true spherical bead-like polymer with a diameter of 20 μm was obtained in a yield of 82%, and a coated plate was produced in the same manner as in Example 1.

The evaluation results of the bead-shaped polymer of Example 2 are shown in Table 1, and the evaluation results of the coating film made using these beads are shown in Table 2.
Also listed in the table.

Example 3 240 g of ethyl acrylate was mixed with 21 g of butyl acrylate.
Polymerization was carried out in the same manner as in Example 1 except that 0 parts and 30 parts of hydroxyethyl acrylate were used. A true spherical bead-shaped polymer with an average particle diameter of 19 μm was obtained in a yield of 79%, and dried in the same manner as in Example 1. Got beads.

Next, to 50 parts of the beads, 20 parts of an alkyd polyol for two-component urethane paint; Burnock D-128-60 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), and a polyisocyanate for two-component urethane paint; Parnock DN- 98
0 (Dainippon Ink & Chemicals Co., Ltd. a) and 30 parts of toluene were mixed together to prepare a paint. The paint is A
60℃ after roll coating on BS resin to a thickness of approximately 25μm
The plate was baked for 30 minutes to produce a coated board.

The evaluation results of the bead-shaped polymer of Example 3 are shown in Table 1, and the evaluation results of the coating film made using this bead are shown in Table 2.
Also listed in the table.

Example 4 Polymerization was carried out in the same manner as in Example 1 except that the amounts of ethyl acrylate and diethylene glycol dimethacrylate were changed to 295 parts and 5 parts, respectively. A true spherical bead-like polymer with an average particle diameter of 23 μm was obtained in a yield of 85%. A coated plate was prepared in the same manner as in Example 1.

The evaluation results of the bead-shaped polymer of Example 4 are shown in Table 1, and the evaluation results of the coating film made using these beads are shown in Table 2.
Also listed in the table.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that methyl methacrylate was used instead of ethyl acrylate and ethylene glycol methacrylate was used instead of diethylene glycol dimethacrylate. The average particle size was 25 μm.
Example 1 A true spherical bead-like polymer was obtained with a yield of 75%.
A painted board was prepared in the same manner.

The evaluation results of the bead-shaped polymer of Comparative Example 1 are shown in Table 1, and the evaluation results of the coating film made using this bead are shown in Table 2.
Also listed in the table.

Comparative Example 2 Butyl acrylate instead of ethyl acrylate,
In addition, when polymerization was carried out in the same manner as in Example 1 except that divinylbenzene was used instead of diethylene glycol dimethacrylate, a true spherical bead-like polymer with an average particle diameter of 28 μm was obtained in a yield of 78%, which was the same as in Example 1. A coated plate was prepared.

The evaluation results of the bead-shaped polymer of Comparative Example 2 are shown in Table 1, and the evaluation results of the coating film made using this bead are shown in Table 2.
Also listed in the table.

Comparative Example 3 20 parts of Parnock D-128-60 (Dainippon Ink & Chemicals Co., Ltd.) and Parnock DN-980 (Dainippon Ink & Chemicals Co., Ltd.) were added to 50 parts of the beads obtained in Comparative Example 2. A paint was prepared by mixing 30 parts of toluene and 30 parts of toluene.
After applying roll coating to a thickness of , baking treatment was performed at 60° C. for 30 minutes to produce a coated board.

The evaluation results of the coating film of Comparative Example 3 are listed in Table 2.

Comparative Example 4 Polymerization was carried out in the same manner as in Example 1 except that the amounts of ethyl acrylate and diethylene glycol dimethacrylate were changed to 299 parts and 1 part, respectively. A true spherical bead-like polymer with an average particle diameter of 23 μm was obtained in a yield of 85%. Obtained.

The evaluation results of the bead-shaped polymer of Comparative Example 4 are also listed in Table 1.

Comparative Example 5 Polymerization was carried out in the same manner as in Example 1 except that the amounts of ethyl acrylate and diethylene glycol dimethacrylate were changed to 150 parts and 50 parts, respectively. A true spherical bead-shaped polymer with an average particle diameter of 19 μm was obtained in a yield of 73%. Obtained.

The evaluation results of the bead-shaped polymer of Comparative Example 5 are shown in Table 1, and the evaluation results of the coating film made using this bead are shown in Table 2.
Also listed in the table.

Blanks in Table 2 are Acridic A-157
(manufactured by Dainippon Ink & Chemicals Co., Ltd.) and no beads were added.

From the evaluation results shown in Tables 1 and 2, the bead-shaped polymers (Examples 1, 2, 3 and 4) that satisfy the present invention are as follows:
It is highly soft, has excellent solvent resistance and heat resistance, and when added to paints, it can produce a noticeable matte effect and a soft wet suede feel, and also has excellent weather resistance. This is clearly understood.

Claims (1)

[Claims] 1. (A) an ester of an alcohol having 2 to 12 carbon atoms and acrylic acid, or an ester of an alcohol having 6 to 12 carbon atoms and methacrylic acid; (B) the following formula (a) or (B) Alkylene glycol or polyalkylene glycol represented by , R_ is OCH2
CH2, OCH(CH3)CH2, OCH(CH3)C
H2CH2 or O-(CH2)6, and n represents an integer of 1 or more and 14 or less. ) In a copolymer mainly composed of (A) component and (B)
The amount of the component is adjusted so that the degree of crosslinking α is 0.01 or more and 0.4 or less (however, α = {(W2/M2)×2}/{(W1/M1)×n1
+(W2/M2)×2}M1: Molecular weight of compound (A) M2: Molecular weight of compound (B) W1: Weight (g) of compound (A) used in polymerization W2: Compound (B) used in polymerization Weight (g) n1: Compound (A
) is used so that the number of vinyl groups in one molecule of ) is within the range of
A bead-shaped polymer characterized by having the physical properties of a) to (c). (a) Elastic modulus (E') 1×10^5≦E'≦1×10^8 (dyn/cm^2
) (b) Glass transition temperature (Tg) -80≦Tg≦20 (℃
) (c) Particle size (D) 0.5≦D≦300 (μm) 2. (A) Alcohol with 2 to 12 carbon atoms and acrylic acid, or alcohol with 6 to 12 carbon atoms and methacrylic acid and (B) alkylene glycol or polyalkylene glycol represented by the following formula (a) or (b) (b) (However, X is H or CH3, R_1 is OCH
2CH2,OCH(CH3)CH2,OCH(CH3)
CH2CH2 or O-(CH2)6, and n represents an integer of 1 to 14. ) and (C) Alcohol represented by the following general formula (c); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (c) (However, X is H or CH3, and R2 has 2 to 2 carbon atoms. In the copolymer whose main component is Component (A), Component (C), and Component (B), the degree of crosslinking α is 0.01 or more and 0.4 or less (however, α = {(W2/M2)×2}/{(W1/M1)×n1
+(W2/M2)×2}M1: Average molecular weight of compounds (A) and (C) expressed by the following formula; M1=MA×(WA)/(WA+WC)+MC×(WC
)/(WA+WC)MA: Molecular weight of compound (A) MC: Molecular weight of compound (C) WA: Weight of compound (A) used in polymerization (g) WC: Weight of compound (C) used in polymerization (g) ) M2: Compound (B
) molecular weight W1: total weight (g) of compounds (A) and (C) used in polymerization
) W2: weight (g) of compound (B) used for polymerization n1: number of vinyl groups in one molecule of compound (A)
A bead-shaped polymer characterized by having the physical properties of a) to (d). (a) Elastic modulus (E') 1×10^5≦E'≦1×10^8 (dyn/cm^2
) (b) Glass transition temperature (Tg) -80≦Tg≦20 (℃
) (c) Hydroxyl group density (q_O_H) 0.01≦q_O_H≦20 (meq/g) (d) Particle diameter (D) 0.5≦D≦300 (μm)