JPH0873535A - Production of thermoplastic resin - Google Patents

Abstract

PURPOSE: To provide a process for producing a thermoplastic resin which has both thermolasticity and high mechanical strengths. CONSTITUTION: In producing a thermoplastic resin by copolymerizing a polymerizable monomer mixture contg. a polyvalent metal salt of an org. carboxylic acid having a polymerizable double bond and a vinyl monomer, the copolymn. is conducted in the presence of an org. carboxylic acid compd. having no polymerizable double bond.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing a thermoplastic resin. More specifically, it is excellent in heat resistance, molding processability, mechanical properties and transparency, and a method for producing a thermoplastic resin useful as a molding material, and a thermoplastic resin useful as an acrylic elastomer excellent in molding processability and mechanical properties. And a thermoplastic resin useful as a pressure-sensitive adhesive having excellent heat resistance, viscosity characteristics upon heating and melting, cohesive strength at room temperature, adhesive strength, tackiness and other adhesive characteristics.

[0002]

2. Description of the Related Art Conventionally, a method for producing a (meth) acrylic resin by copolymerizing a polymerizable monomer mixture consisting of an aliphatic ester compound of (meth) acrylic acid and a metal salt of di (meth) acrylic acid There are various proposals.

For example, JP-A-56-74110 discloses an alkyl ester of (meth) acrylic acid and a metal salt of a polymerizable unsaturated carboxylic acid (Mg, Al, Sn, Pb,
Zn, Ce, Ti, Zr, Hf, V, Cr), and a method of producing an ion-crosslinked acrylic resin by radically polymerizing a monomer mixture containing another comonomer in bulk.

In the above publication, the methacrylic resin containing methyl methacrylate as a main component is excellent in weather resistance and transparency, and is well balanced in mechanical properties and thermal properties. It is widely used for parts, electric equipment parts, and the like.

However, the molding processability when imparting heat resistance to such a methacrylic resin is not always sufficient, and it cannot be said to be a method for producing a resin useful as a molding material.

As a method of improving the molding processability of methacrylic resin, lowering the molecular weight of the resin, increasing the copolymerization rate, or adding a large amount of additives such as plasticizers is carried out. There is.

However, although the methacrylic resin thus obtained is certainly improved in molding processability, it has a drawback that heat resistance and mechanical properties are remarkably deteriorated.

Therefore, it has been difficult to obtain a methacrylic resin having both excellent heat resistance and moldability by the conventional method.

Further, in JP-A-56-74110, the acrylic elastomer containing ethyl acrylate as a main component is excellent in heat resistance, ozone resistance, oil resistance, etc., and therefore, oil seals, O-rings, gaskets, etc. It is widely used for packings, hoses for automobiles, etc. Since the monomer unit derived from the acrylate ester in these acrylic elastomers does not have a double bond, it has been conventionally practiced to copolymerize a monomer having an active group serving as a crosslinking point. As such a crosslinking monomer, a halogen group-containing compound, an epoxy group-containing compound, a diene compound and the like are known.

However, acrylic elastomers containing these crosslinking monomers are generally vulcanized with amines, ammonium salts, soap-sulfur and sulfur. The vulcanized acrylic elastomer did not exhibit thermoplasticity because it had a three-dimensional chain formed by vulcanization.

On the other hand, thermoplastic elastomers have the characteristics of exhibiting thermoplasticity at the time of high-temperature processing, and at the same time exhibiting rubber elasticity and high strength at room temperature. Conventional thermoplastic elastomers are polystyrene type, Since most block copolymers such as polyolefins are used, they do not have the characteristics of the acrylic elastomer containing ethyl acrylate as a main component as described above.

Further, JP-A-5-202345 discloses an acrylic hot-melt adhesive resin by copolymerizing a (meth) acrylic vinyl monomer and a metal salt of (meth) acrylic acid. Methods of synthesis are described. Further, JP-A-58-125774 discloses an organic polymer containing at least one carboxylic acid group per polymer molecule, preferably a monomer residue of an alkyl ester of (meth) acrylic acid and a carboxylic acid-containing monomer residue. A composition for a pressure-sensitive hot melt adhesive is described, which comprises an organic polymer containing C, at least one miscible metal salt selected from Zn, Cd, and Zr, and o-methoxyaryl acid. According to these publications, the acrylic hot-melt adhesive resin has excellent light resistance, weather resistance, durability, heat resistance, transparency, good adhesion, and good balance between tackiness and holding power. It is a thing.

However, in such an acrylic hot melt type adhesive resin, when it is heated and melted (for example, 18
Melt viscosity at 0 ° C.) is 30,000 cP or more,
The viscosity characteristics during heating and melting were extremely poor.

In any case, none of these resins has a thermoplastic resin that is compatible with both thermoplasticity and mechanical strength.

[0015]

DISCLOSURE OF THE INVENTION The present invention is to solve the above-mentioned various problems at one time which the conventional methacrylic resin for molding, acrylic elastomer and acrylic hot-melt adhesive resin have. . Therefore, an object of the present invention is to provide a method for producing a thermoplastic resin capable of satisfying both mechanical strength and thermoplasticity (molding processability, viscosity characteristics during heating and melting) so that it can be applied to any of the following, that is, Thermoplastic resin useful as a molding material, which is excellent in heat resistance, molding processability, mechanical properties, transparency, thermoplastic resin useful as an acrylic elastomer excellent in molding processability, mechanical properties, and further heat resistance, It is an object of the present invention to provide a production method applicable to any thermoplastic resin useful as an adhesive having excellent viscosity characteristics at the time of heating and melting, cohesive strength at room temperature, adhesive strength, tackiness and other adhesive characteristics.

[0016]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a polyvalent metal salt compound (A) of an organic carboxylic acid having a polymerizable double bond and a vinyl monovalent compound. Organic carboxylic acid compound (C) having no polymerizable double bond in the polymerizable monomer mixture containing the monomer (B)
By coexisting with each other, more specifically, by appropriately selecting and copolymerizing various component compositions and blending ratios of these (A) to (C), a wide range of applications as exemplified below can be obtained. Suitable thermoplastic resin, that is, the heat resistance derived from polyvalent metal is retained without impairing the properties such as transparency and mechanical properties of the thermoplastic resin obtained by copolymerizing the polymerizable monomer mixture. A thermoplastic resin for molding materials whose molding processability has been remarkably improved, and while maintaining the properties of acrylic elastomer such as heat resistance, ozone resistance, and oil resistance, it has excellent molding processability and mechanical properties. Maintains adhesive properties such as thermoplastic resin as an elastomer, and light resistance, weather resistance, durability, heat resistance, transparency, adhesiveness, balance between tackiness and holding power that acrylic adhesive resin has While, onsets seen that thermoplastic resins for excellent adhesive viscosity characteristics during heat melting is obtained, and have completed the present invention.

That is, the object of the present invention is (1) a polymerizable monomer comprising a polyvalent metal salt compound of an organic carboxylic acid having a polymerizable double bond (A) and a vinyl monomer (B). When a thermoplastic resin is produced by copolymerizing a mixture, a method for producing a thermoplastic resin is characterized in that an organic carboxylic acid compound (C) having no polymerizable double bond is coexisted. It

Another object of the present invention is (2) the polyvalent metal salt compound (A) of an organic carboxylic acid having a polymerizable double bond is a polyvalent metal salt compound of (meth) acrylic acid. It is also achieved by the manufacturing method shown in the above (1).

Another object of the present invention is that (3) the vinyl monomer (B) contains at least one compound selected from the group consisting of (meth) acrylic acid ester compounds and styrene. It is also achieved by the manufacturing method shown in 1) or (2).

Another object of the present invention is that (4) copolymerization is carried out in the presence of water in a proportion of 0.005 to 0.3 mol based on 1 mol of the vinyl monomer (B). It is also achieved by the manufacturing method shown in any one of the above (1) to (3).

Another object of the present invention is (5) one of the above (1) to (4), wherein the vinyl monomer (B) contains methyl methacrylate as a main component. It is also achieved by the manufacturing method shown.

Another object of the present invention is that (6) the vinyl monomer (B) has a glass transition temperature of -100 to 20 ° C. in the polymer obtained from the vinyl monomer (B). It is also achieved by the manufacturing method shown in any one of (1) to (4) above.

Another object of the present invention is (7) any one of the above (1) to (4), wherein the vinyl monomer (B) contains ethyl acrylate as a main component. It is also achieved by the manufacturing method shown.

Another object of the present invention is (8), wherein the vinyl monomer (B) is mainly composed of n-butyl acrylate and / or 2-ethylhexyl acrylate. It is also achieved by the manufacturing method shown in any one of (4) to (4).

Further, the constitution of the present invention for achieving the above object will be described in detail below.

First, a polymerizable monomer mixture containing the polyvalent metal salt compound (A) of an organic carboxylic acid having a polymerizable double bond and the vinyl monomer (B) in the present invention (hereinafter, simply referred to as "polymerization"). (Also referred to as a mixture of polymerizable monomers), a polyvalent metal salt compound (A) of an organic carboxylic acid having a polymerizable double bond
The ratio of the polyvalent metal salt compound (A) may be, but not limited to, 0.2 to 40 mol%, preferably 1.0 to 30 mol%. preferable. When the proportion of the polyvalent metal salt compound (A) is less than 0.2 mol%, it is not preferable because heat resistance derived from the polyvalent metal cannot be maintained, and when it exceeds 40 mol%.
Molding processability and adhesive properties are unfavorably deteriorated.

The proportion of the vinyl monomer (B) in the polymerizable monomer mixture in the present invention is not particularly limited, but 60 to 99.8 mol%, preferably 70 to 99.0.
It is preferably in the range of mol%. When the proportion of the vinyl monomer (B) is less than 60 mol%, it is not preferable because the original characteristics of the (meth) acrylic resin cannot be maintained, and when it exceeds 99.8 mol%, other components are not contained. Since the content is limited, the thermoplasticity and the mechanical strength, which are the features of the present invention, cannot be achieved at the same time, which is not preferable.

In producing a thermoplastic resin by copolymerizing a polymerizable monomer mixture in the present invention, an organic carboxylic acid compound (C) having no polymerizable double bond (hereinafter, simply referred to as an organic carboxylic acid compound (C (Also referred to as)) is present in the polymerization system for copolymerization. The organic carboxylic acid compound (C) is used in an amount of 0.1 to 4 mol per 1 mol of the polyvalent metal salt compound (A). It is preferable to coexist and coexist at a ratio of preferably 0.3 to 2 mol. If the ratio of the organic carboxylic acid compound (C) to 1 mol of the polyvalent metal salt compound (A) exceeds 4 mol, the performance such as heat resistance derived from the polyvalent metal salt may be insufficient, or the polymerizable monocarboxylic acid compound (C) may not be polymerized. There are problems that insoluble matter is generated in the monomer mixture and uniform copolymerization cannot be performed, and the obtained thermoplastic resin becomes opaque. When the ratio of the organic carboxylic acid compound (C) to 1 mol of the polyvalent metal salt compound (A) is less than 0.1 mol, the moldability of the thermoplastic resin obtained may be insufficient.

In the present invention, when the polymerizable monomer mixture is copolymerized to produce the thermoplastic resin, it is preferable that the organic carboxylic acid compound (C) and water are coexisted in the polymerization system. The amount of water added is preferably 0.005 to 0.3 mol, and more preferably 0.005 to 0.1 mol, based on 1 mol of the vinyl monomer (B). When the amount of water added is less than 0.005 mol with respect to 1 mol of the vinyl monomer (B), the amount of the polyvalent metal salt compound (A) that can be introduced into the obtained resin is limited, In addition to insufficient mechanical properties and adhesive properties of the resin such as heat resistance derived from metal, the resulting resin may become opaque, which is not preferable. Further, when the amount of water added exceeds 0.3 mol with respect to 1 mol of the vinyl monomer (B), insoluble matter is generated in the polymerizable monomer mixture, and uniform copolymerization cannot be performed. It is not preferable because it may occur.

As the polyvalent metal constituting the polyvalent metal salt compound (A) used in the present invention, for example, beryllium, magnesium, calcium, barium, manganese,
Examples thereof include cobalt, nickel, zinc, cadmium, aluminum and the like. Of these, zinc is preferably used.

Examples of the polyvalent metal salt compound (A) include acrylic acid polyvalent metal salt compounds, methacrylic acid polyvalent metal salt compounds, undecenoic acid polyvalent metal salt compounds, and oleic acid polyvalent metal salt compounds. Examples thereof include a valent metal salt compound, a polyvalent metal salt compound of crotonic acid, and a polyvalent metal salt compound of cinnamic acid. Of these, zinc diacrylate and zinc dimethacrylate are preferably used.

The vinyl monomer (B) used in the present invention is not particularly limited as long as it is copolymerizable with the polyvalent metal salt compound (A), and for example, methyl (meth) acrylate, Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate,
N-Butyl (meth) acrylate, t (meth) acrylic acid
-Butyl, sec-butyl (meth) acrylate, pentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, ( Aliphatic ester compounds of (meth) acrylic acid such as octadecyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate, fragrance of (meth) acrylic acid such as benzyl (meth) acrylate and phenyl (meth) acrylate Group ester compounds, ethylene, propylene,
Olefin-based hydrocarbons such as vinyl chloride or halogen-substituted products thereof, aromatic vinyl compounds such as styrene and methylstyrene, vinyl ester compounds of monovalent carboxylic acids such as vinyl acetate and vinyl propionate, (meth) allyl alcohol , Unsaturated alcohol compounds such as croton alcohol, α, β-ethylenically unsaturated carboxylic acid compounds such as (meth) acrylic acid, crotonic acid and cinnamic acid, unsaturated dibasic carboxylic acids such as maleic acid, fumaric acid and itaconic acid Acid, monoester compounds of monohydric alcohols such as maleic acid monomethyl ester, maleic acid monoallyl ester and unsaturated dibasic carboxylic acid, divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacryle , Polyvinyl compounds such as trimethylolpropane trimethacrylate and diallyl maleate, 2 (N, N-dimethylamino) ethyl acrylate, 2 (N, N-dimethylamino) ethyl methacrylate, 2 (N, N-diethylamino) ethyl Acrylate, amine compounds such as 2 (N, N-diethylamino) ethyl methacrylate, 2-vinylpyridine,
3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 2-vinyl-5-ethylpyridine, 2-vinylquinoline, 1-vinylcarbazole, 3-vinyl Carbazole, 1-methyl-3-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 4-vinylimidazole, 4-vinylpyrimidine, 1-methacryloylaziridine, 2- (1-aziridinyl) ethylmethacrylate, 4-acryloyloxy. -2,2,6,6-
Tetramethylpiperidine, 4-methacryloyloxy-
2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-methacryloyloxy-1,2,2,6
6-pentamethylpiperidine, 9-aza-3-acryloyloxymethyl-3-ethyl-8,8,10,10-
Examples thereof include nitrogen atom-containing organic heterocyclic compounds such as tetramethyl-1,5-dioxa-spiro [5.5] undecane, and of these, one kind or two or more kinds can be used, but preferably , Other than the aliphatic ester compound of (meth) acrylic acid as a main component and the aliphatic ester compound of (meth) acrylic acid in the vinyl monomer (B), the polymerizability of the other vinyl monomer (B) The proportion in the monomer mixture is 0 to 20 mol%, preferably 0 to 15 mol%. The ratio of the other vinyl monomer (B) is 20
When it exceeds mol%, the characteristics of the (meth) acrylic resin cannot be sufficiently exhibited, which is not preferable. Furthermore, more preferably, it is appropriately selected from these, depending on the intended use.

That is, when the thermoplastic resin is used as a general (general purpose) molding material (structure) required to have mechanical properties such as impact strength and surface hardness, heat resistance, molding processability and transparency. Has a relatively high glass transition temperature (20
To 130 ° C), for example, methyl methacrylate (104 ° C), ethyl methacrylate (66 ° C), n-propyl methacrylate (35 ° C) isopropyl methacrylate (81 ° C), t-butyl methacrylate (107 ° C). ),
T-Butyl acrylate (43 ° C) methacrylic acid sec-
Butyl (60 ° C), cyclohexyl methacrylate (66
C.), benzyl methacrylate (54.degree. C.), phenyl methacrylate (110.degree. C.), 2-hydroxyethyl methacrylate (55.degree. C.), styrene or methylstyrene and the like are desirable. In this case, the basic properties as the thermoplastic resin for the molding material (structure) according to the present invention, such as the balance between weatherability, transparency and heat resistance of the resin for molding material (structure) to be obtained, and moldability In order to maintain the content of (meth) acrylic monomer, it is preferable that the (meth) acrylic monomer is contained in a proportion of 80 to 100 mol%, and methyl methacrylate is the main component (50
Mol% or more) is preferable. The temperature in parentheses after the exemplified substances (monomers) of the vinyl monomer (B) indicates the glass transition temperature (Tg) of the homopolymer of each exemplified substance.

When the thermoplastic resin is used as an acrylic elastomer or an adhesive, the vinyl monomer (B) has a glass transition temperature of -100 to 20 ° C., which is a polymer obtained from the vinyl monomer (B). The range of is preferable.

The glass transition temperature of the polymer obtained from the vinyl monomer (B) is a mixture (component 1 to component n) in which the vinyl monomer (B) is n or more components (n is an integer of 2 or more).
In the case of, the glass transition temperature is expressed by the Fox equation (1) 1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + ... (+ W _n / Tg _n ) (1) (where Tg is a vinyl monomer ( The glass transition temperature of the polymer obtained from the mixture of B), Tg ₁ is the glass transition temperature of the homopolymer of component 1 of the vinyl monomer (B), Tg
₂ Glass transition temperature, Tg _n of the homopolymer of component 2 of a vinyl monomer (B) is a glass transition temperature of the homopolymer of component n of the vinyl monomer (B). W ₁ is the weight fraction of component 1 of the vinyl monomer (B), W ₂ is the weight fraction of component ₂ of the vinyl monomer (B), W _n is the component of vinyl monomer (B) The weight fraction of n is shown. ) Is used.

When the thermoplastic resin is used as an acrylic elastomer which is required to have moldability while maintaining various properties including mechanical properties such as tensile strength and elongation at break of the acrylic elastomer, Having a relatively low glass transition temperature, for example, methyl acrylate (8 ° C.), ethyl acrylate (-24 ° C.), isopropyl acrylate (-3 to −6 ° C.) to acrylic acid s
Those having ec-butyl (-22 ° C) as a main component are desirable. In this case, the vinyl monomer (B) contains 50 mol% or more of ethyl acrylate, preferably 80 mol%.
It is preferably contained in the above proportion. When the proportion of the component is less than 50 mol%, basic properties as an elastomer (thermoplastic resin) according to the present invention such as balance between oil resistance, weather resistance and mechanical properties of the obtained elastomer and molding processability. May be insufficiently retained. When used as an elastomer, the glass transition temperature of the polymer obtained from the vinyl monomer (B) is -70.
-20 ° C, preferably -50 to 0 ° C is desirable.
If it exceeds 20 ℃, it may not show rubber elasticity.
If the temperature is lower than -70 ° C, the mechanical strength may be insufficient.

Further, the thermoplastic resin has an adhesive force at room temperature,
When used as a pressure-sensitive adhesive required for cohesive strength, tackiness such as tackiness, heat resistance, and viscosity characteristics upon heating and melting, for example, n-butyl acrylate and / or 2-ethylhexyl acrylate is mainly used. The component is preferable, and the ratio of these components is more preferably 80 mol% or more. When the proportion of the component is less than 50 mol%, the resulting resin has light resistance, weather resistance, durability, heat resistance, transparency, adhesiveness, adhesive properties such as balance between tackiness and holding power, and heating. Insufficient retention of basic properties such as the viscosity property when melted as the thermoplastic resin for the pressure-sensitive adhesive according to the present invention may be insufficient. When used as an adhesive, the polymer obtained from the vinyl monomer (B) has a glass transition temperature of −100 to −20 ° C., preferably −90 to −40 ° C. The glass transition temperature of the polymer obtained from the vinyl monomer (B) is -10.
If the temperature is lower than 0 ° C, the adhesive properties may be impaired,
If it exceeds -20 ° C, the viscosity characteristics upon heating may be impaired.

Examples of the organic carboxylic acid compound (C) used in the present invention include saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid and hexanoic acid, and saturated oxalic acid, malonic acid and succinic acid. Carbocyclic carboxylic acids such as aliphatic dicarboxylic acids, cyclohexylcarboxylic acid, benzoic acid, toluic acid, salicylic acid, naphthoic acid, phthalic acid and cinnamic acid, and heterocyclic carboxylic acids such as furancarboxylic acid, thiophenecarboxylic acid and pyridinecarboxylic acid , High molecular weight carboxylic acids such as polyacrylic acid, polymethacrylic acid and the like, and one or more of these compounds are used. Particularly preferred are saturated aliphatic monocarboxylic acids and carbocyclic carboxylic acids. The molecular weight of the organic carboxylic acid compound (C) is preferably less than 10,000. If the molecular weight exceeds 10,000,
There is a possibility that sufficient reactivity may not be expressed due to steric hindrance or the like.

The thermoplastic resin of the present invention is obtained by copolymerizing a polymerizable monomer mixture to produce a thermoplastic resin, and by coexisting an organic carboxylic acid compound (C) in a polymerization system. To be To allow the organic carboxylic acid compound (C) to coexist in the polymerization system, for example, the polycarboxylic acid salt compound (A) and / or the vinyl monomer (B) are mixed with the organic carboxylic acid compound (C) in advance. It is possible to employ a method of placing it, a method of adding the organic carboxylic acid compound (C) to the polymerization vessel at the time of polymerization, and mixing with the polymerizable monomer mixture.
Above all, it is preferable to first mix the organic carboxylic acid compound (C) with the vinyl monomer (B) and then mix the polyvalent metal salt compound (A).

In addition, when the organic carboxylic acid compound (C) is allowed to coexist in the polymerization system and water is allowed to coexist when a thermoplastic resin is produced by copolymerizing a polymerizable monomer mixture, for example, a polycarboxylic acid The valent metal salt compound (A) and / or the vinyl monomer (B) is previously added to the organic carboxylic acid compound (C).
And a method of mixing water with water, a method of adding an organic carboxylic acid compound (C) and water to a polymerization vessel at the time of polymerization, and mixing with a polymerizable monomer mixture can be adopted. Above all, it is preferable to first mix the organic carboxylic acid compound (C) and water with the vinyl monomer (B) and then mix the polyvalent metal salt compound (A).

The copolymerization in the present invention can be carried out by a known polymerization method, but a radical polymerization method is preferably used. As the polymerization initiator, a generally known free radical catalyst, for example, benzoyl peroxide, lauroyl peroxide, tertiary butyl hydroxyperoxide, cumene peroxide, methyl ethyl ketone peroxide, tertiary butyl perphthalate, caproyl peroxide is used. Organic peroxides such as, potassium persulfate, sodium persulfate, inorganic oxides such as hydrogen peroxide, azobisisobutyronitrile,
Azobisisobutyramide, 2,2'-azobis (2,2
Examples thereof include azo compounds such as 4-dimethylvaleronitrile), azobis (α-methylvaleronitrile), and azobis (α-methylbutyronitrile). Among these, one kind or two or more kinds can be used. . These polymerization initiators are added to the polymerizable monomer mixture at 0.0
It can be appropriately used within a range of 1 to 10% by weight, preferably 0.1 to 8% by weight. If the polymerization initiator is less than 0.01% by weight, the concentration of the initiator in the polymerization system is insufficient,
It is not preferable because the reaction yield in the whole system becomes low, and if it exceeds 10% by weight, further effect commensurate with the addition cannot be obtained, which is uneconomical.

In the present invention, lauryl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, 2-mercaptoacetic acid, carbon tetrachloride and carbon tetrabromide are used to control the molecular weight of the thermoplastic resin obtained by copolymerization. Chain transfer agents may be used.

There are no particular restrictions on the polymerization mode that can be used in the production method of the present invention, and known polymerization modes such as bulk polymerization, suspension polymerization, emulsion polymerization and solution polymerization can be used. Can be adopted. Then, various additives such as a suspending agent and an emulsifier can be used according to these polymerization forms, and the type and amount of the polymerization initiator and the chain transfer agent, the polymerization conditions such as the polymerization temperature and the pressure may be appropriately determined. Good. Particularly when a thermoplastic resin for a molding material is obtained by copolymerization, a cast polymerization method, which is one of the bulk polymerization methods, is preferably used because a highly transparent thermoplastic resin can be easily obtained.

In the production method of the present invention, carbon, fumed silica, wet silica, talc, clay-based filler, quartz powder, diatomaceous filler may be used as a reinforcing filler before or after the polymerization, if necessary. One kind or two or more kinds such as soil can be mixed and used. As the dispersant, one kind or two or more kinds of low molecular weight siloxane, silanol group-containing silane, alkoxysilane and the like can be mixed and used. Comolec No. as a plasticizer Two oils, one kind or two or more kinds such as Sunper 2280 and PW-380 can be mixed and used. As an anti-aging agent, Noward 455, Irganox 1010, Nocrac 224,
One kind or two or more kinds of Nocrac White, Nocrac 630F, Nocrac 810NA, Antige OD and the like can be mixed and used. In addition to these, various additives such as a colorant, a modifier, a stabilizer, a bulking agent, and a release agent can be mixed and used, if necessary.

[0045]

In the production method of the present invention, an organic carboxylic acid compound (C) having no polymerizable double bond is allowed to coexist in the polymerizable monomer mixture and copolymerized. Due to the coexistence of the organic carboxylic acid compound (C), a part (terminal portion) of the crosslinked structure formed between the linear polymer of the vinyl monomer (B) and the polyvalent metal salt compound (A) is not bonded. Since there is a partially uncrosslinked linear polymer that can be made into a state, the mechanical strength due to the crosslinked structure and the thermoplasticity due to the presence of the uncrosslinked linear polymer (molding processability, viscosity characteristics during heating and melting) It is compatible.

[0046]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these.

Example 1 1.2 g (0.005 mol) of zinc dimethacrylate was mixed and dissolved in 99 g (0.99 mol) of methyl methacrylate. After 0.35 g (0.0025 mol) of salicylic acid was added and dissolved in this solution, 0.5 g of azobisisobutyronitrile as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, and after polymerization at 70 ° C. for 4 hours,
After curing at 120 ° C. for 2 hours, a resin (1) was obtained.

Example 2 0.14 g (0.0006 mol) of 4-acryloyl-1,2,2,6,6-pentamethylpiperidine was dissolved in 99 g (0.99 mol) of methyl methacrylate, followed by hexane. 1.2 g (0.01 mol) of acid and 2.4 g (0.01 mol) of zinc dimethacrylate were mixed and dissolved. 0.5 g of benzoyl peroxide as a radical polymerization initiator in this solution
Was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket,
After polymerization at 0 ° C. for 4 hours, post-curing was performed at 120 ° C. for 2 hours to obtain resin (2).

Example 3 To 99 g (0.99 mol) of methyl methacrylate,
Water was added and dissolved so that the water content was 0.1 g (0.0055 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 1.2 g (0.01 mol) of benzoic acid and 2.4 g (0.01 mol) of zinc dimethacrylate were mixed and dissolved. To this solution, 0.5 g of benzoyl peroxide was added and dissolved as a radical polymerization initiator. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 80 ° C. for 4 hours, and post-cured at 120 ° C. for 2 hours to obtain a resin (3).

Example 4 With respect to 98 g (0.98 mol) of methyl methacrylate,
Water was added and dissolved so that the water content was 0.1 g (0.0055 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Further, 0.94 g (0.006 mol) of 2 (N, N-dimethylamino) ethyl methacrylate was dissolved. 2.3 g (0.02 mol) of hexanoic acid and 4.1 g (0.02 mol) of zinc diacrylate were mixed and dissolved in this solution. To this solution, 0.5 g of lauroyl peroxide as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 70 ° C. for 4 hours, and post-cured at 120 ° C. for 2 hours to obtain a resin (4).

Example 5 A mixture of 67 g (0.67 mol) of methyl methacrylate and 8.6 g (0.12 mol) of acrylic acid had a water content of 3.6 g (0.2 mol). Water was added to and dissolved. The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 14 g (0.06 mol) of 4-acryloyl-1,2,2,6,6-pentamethylpiperidine was dissolved. 28 g (0.2 mol) of salicylic acid and 44 g (0.21 mol) of zinc diacrylate were mixed and dissolved in this solution. To this solution, 0.5 g of azobisisobutyronitrile as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 70 ° C. for 4 hours, and post-cured at 120 ° C. for 2 hours to obtain a resin (5).

Example 6 With respect to 67 g (0.67 mol) of methyl methacrylate,
Water was added and dissolved so that the water content was 0.81 g (0.045 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 4-acryloyl-1,2,2,6,6
48 g (0.2 mol) of pentamethylpiperidine were dissolved. 42 g (0.3 mol) of salicylic acid and 78 g (0.33 mol) of zinc dimethacrylate were mixed and dissolved in this solution. To this solution, 0.5 g of azobisisobutyronitrile as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, and polymerized at 70 ° C for 4 hours, then at 120 ° C.
After curing for 2 hours, a resin (6) was obtained.

Comparative Example 1 1.2 g (0.005 mol) of zinc dimethacrylate was mixed and dissolved in 99 g (0.99 mol) of methyl methacrylate. To this solution, 0.5 g of azobisisobutyronitrile as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, and polymerized at 70 ° C for 4 hours, then at 120 ° C.
After that, the resin was post-cured for 2 hours to obtain a resin (1) for comparison.

Comparative Example 2 0.14 g (0.0006 mol) of 4-acryloyl-1,2,2,6,6-pentamethylpiperidine was dissolved in 99 g (0.99 mol) of methyl methacrylate and then di 2.4 g (0.01 mol) of zinc methacrylate was mixed and dissolved. To this solution, 0.5 g of benzoyl peroxide was added and dissolved as a radical polymerization initiator. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 80 ° C. for 4 hours, and post-cured at 120 ° C. for 2 hours to obtain a resin (2) for comparison. It was

Comparative Example 3 With respect to 99 g (0.99 mol) of methyl methacrylate,
Water was added and dissolved so that the water content was 0.1 g (0.0055 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 2.4 g of zinc dimethacrylate (0.01
Mol) were mixed and dissolved. To this solution, 0.5 g of benzoyl peroxide was added and dissolved as a radical polymerization initiator. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, and after polymerization at 80 ° C. for 4 hours,
After curing at 120 ° C. for 2 hours, a resin (3) for comparison was obtained.

Comparative Example 4 With respect to 98 g (0.98 mol) of methyl methacrylate,
Water was added and dissolved so that the water content was 0.1 g (0.0055 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Further, 0.94 g (0.006 mol) of 2 (N, N-dimethylamino) ethyl methacrylate was dissolved. 4.1 g (0.02 mol) of zinc diacrylate was mixed and dissolved in this solution. To this solution, 0.5 g of lauroyl peroxide as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, and the mixture was polymerized at 70 ° C. for 4 hours and then 1
After curing at 20 ° C. for 2 hours, a resin (4) for comparison was obtained.

Comparative Example 5 A mixture of 67 g (0.67 mol) of methyl methacrylate and 8.6 g (0.12 mol) of acrylic acid had a water content of 3.6 g (0.2 mol). Water was added to and dissolved. The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 14 g (0.06 mol) of 4-acryloyl-1,2,2,6,6-pentamethylpiperidine was dissolved. To this solution, 44 g (0.21 mol) of zinc diacrylate was mixed and dissolved. To this solution, 0.5 g of azobisisobutyronitrile as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, and the mixture was polymerized at 70 ° C for 4 hours.
After curing at 0 ° C. for 2 hours, a resin (5) for comparison was obtained.

Comparative Example 6 With respect to 67 g (0.67 mol) of methyl methacrylate,
Water was added and dissolved so that the water content was 0.81 g (0.045 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 4-acryloyl-1,2,2,6,6
48 g (0.2 mol) of pentamethylpiperidine were dissolved. 78 g (0.33 g) of zinc dimethacrylate was added to this solution.
Mol) were mixed and dissolved. To this solution, 0.5 g of azobisisobutyronitrile as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 70 ° C. for 4 hours, and post-cured at 120 ° C. for 2 hours to obtain a comparative resin (6). It was

Example 7 Resins (1) to (6) of the present invention obtained in Examples 1 to 6
And the comparative resins (1) obtained in Comparative Examples 1 to 6
Using (6), heat resistance, moldability, mechanical properties, and transparency were evaluated. The results are as shown in Table 1.

[Evaluation Method] The heat resistance was evaluated by measuring the glass transition temperature with a resin having a thickness of 1 mm using a thermomechanical analyzer (TMA120C manufactured by Seiko Denshi Kogyo KK).

Moldability was measured by using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 230 ° C. and 10 kgf.
The weight (MI value) of the resin that flowed for 10 minutes under the conditions of was measured and evaluated.

Mechanical properties were evaluated by measuring impact strength and surface hardness. The impact strength was measured by measuring the Izod impact strength of the resin processed into No. 1 test piece A notch (JIS K 7110) using an Izod impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.). The surface hardness was measured and evaluated for a resin having a thickness of 1 mm using an electric pencil hardness tester (manufactured by Yasuda Seiki Co., Ltd.).

The transparency was evaluated by measuring the total light transmittance of a resin having a thickness of 2 mm using a haze meter (SZ-Sigma 90 type manufactured by Nippon Denshoku Industries Co., Ltd.). Table 1 shows the results.

[0064]

[Table 1]

As is clear from Table 1, the resins (1) to (6) obtained by the production method of the present invention were excellent in both heat resistance and moldability. Furthermore, the mechanical properties and transparency were excellent.

However, the resins (1) to (6) for comparison are 2
It did not flow at 30 ° C. at all, and the moldability was extremely poor.

Example 8 Ethyl acrylate (calculated glass transition temperature of polymer obtained from this monomer is -24 ° C.) 10
Water content is 0.09g for 0g (1.0mol)
Water was added and dissolved so as to be (0.005 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Further, 1.2 g (0.005 mol) of zinc dimethacrylate and 0.29 g (0.0025 mol) of hexanoic acid were mixed and dissolved, and then 0.5 g of azobisisobutyronitrile was added and dissolved as a radical polymerization initiator. . This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C. for 3 hours, and then post-cured at 80 ° C. for 2 hours to obtain an elastomer (1).

Example 9 Ethyl acrylate (calculated glass transition temperature of polymer obtained from this monomer is -24 ° C) 10
Water content is 0.18g for 0g (1.0mol)
Water was added and dissolved so as to be (0.01 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 1.2 g (0.01 mol) of benzoic acid and 2.4 of zinc dimethacrylate.
g (0.01 mol) were mixed and dissolved. To this solution, 0.5 g of benzoyl peroxide was added and dissolved as a radical polymerization initiator. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, and the mixture was mixed at 60 ° C for 3 hours.
After the polymerization for an hour, it was post-cured at 80 ° C. for 2 hours to obtain an elastomer (2).

Example 10 Ethyl acrylate (calculated glass transition temperature of polymer obtained from this monomer is -24 ° C) 10
Water content is 0.36g for 0g (1.0mol)
Water was added and dissolved so as to be (0.02 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 2.8 g (0.02 mol) of salicylic acid and zinc dimethacrylate 4.
8 g (0.02 mol) were mixed and dissolved. To this solution, 0.5 g of benzoyl peroxide was added and dissolved as a radical polymerization initiator. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C. for 3 hours, and then post-cured at 80 ° C. for 2 hours to obtain an elastomer (3).

Example 11 Ethyl acrylate (Calculated glass transition temperature of the polymer obtained from this monomer is -24 ° C.) 10
With respect to 0 g (1.0 mol), the water content was 0.09 (0.
Water was added and dissolved so that the amount became 005 mol). The amount of water is the Karl Fischer moisture meter (M manufactured by Kyoto Electronics Manufacturing Co., Ltd.
KS-3P type). Further 2 (N, N-
Dimethylamino) ethyl methacrylate 0.94g
(0.006 mol) was dissolved. 2.3 g (0.02 mol) of hexanoic acid and 4.1 g of zinc diacrylate were added to this solution.
(0.02 mol) were mixed and dissolved. To this solution, 0.5 g of lauroyl peroxide as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C. for 3 hours, and then post-cured at 80 ° C. for 2 hours to obtain an elastomer (4).

Example 12 80 g (0.8 mol) of ethyl acrylate and n of acrylic acid
-Butyl 26 g (0.2 mol) mixed solution (calculated glass transition temperature of polymer obtained from these monomers is -28 ° C), water content 0.09 g
Water was added and dissolved so as to be (0.005 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Further, 1.2 g (0.005 mol) of zinc dimethacrylate and 0.29 g (0.0025 mol) of hexanoic acid were added and dissolved, and then 0.5 g of azobisisobutyronitrile was dissolved as a radical polymerization initiator. . This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C. for 3 hours, and post-cured at 80 ° C. for 2 hours to obtain an elastomer (5).

Example 13 Ethyl acrylate (Calculated glass transition temperature of the polymer obtained from this monomer is -24 ° C.) 10
The water content is 1.3 g (0.
Water was added and dissolved so that the amount became 07 mol). The amount of water is the Karl Fischer moisture meter (MK manufactured by Kyoto Electronics Manufacturing Co., Ltd.
S-3P type). Furthermore, 4-acryloyl-1,2,2,6,6-pentamethylpiperidine 42
g (0.18 mol) was dissolved. 68 g (0.49 mol) of salicylic acid and 103 g of zinc dimethacrylate were added to this solution.
(0.44 mol) were mixed and dissolved. 0.8 g of azobisisobutyronitrile as a radical polymerization initiator was added to this solution.
Was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket,
After polymerizing at 0 ° C. for 3 hours, it was post-cured at 80 ° C. for 2 hours to obtain an elastomer (6).

Comparative Example 7 Ethyl acrylate (Calculated glass transition temperature of polymer obtained from this monomer is -24 ° C.) 10
Water content is 0.09g for 0g (1.0mol)
Water was added and dissolved so as to be (0.005 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). After 1.2 g (0.005 mol) of zinc dimethacrylate was added and dissolved in this solution, 0.5 g of azobisisobutyronitrile as a radical polymerization initiator was added and dissolved. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C. for 3 hours, and then post-cured at 80 ° C. for 2 hours to obtain a comparative elastomer (1). It was

Comparative Example 8 Ethyl acrylate (Calculated glass transition temperature of polymer obtained from this monomer is -24 ° C.) 99
Water content is 0.18g with respect to g (0.99mol)
Water was added and dissolved so as to be (0.01 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). 2.4 g (0.01 mol) of zinc dimethacrylate was mixed and dissolved in this solution. To this solution, 0.5 g of benzoyl peroxide was added and dissolved as a radical polymerization initiator. This mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C. for 3 hours, and then post-cured at 80 ° C. for 2 hours to obtain a comparative elastomer (2). It was

Example 14 Elastomers (1) of the present invention obtained in Examples 8 to 13
-(6) and the comparative elastomers (1) and (2) obtained in Comparative Examples 7 to 8 were used to evaluate moldability and mechanical properties. The results are as shown in Table 2.

[Evaluation method] The moldability was 160 using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.).
The weight (MI value) of the elastomer that flowed for 10 minutes under the conditions of ° C and 21.6 kgf was measured and evaluated.

Mechanical properties were evaluated by measuring tensile strength and elongation at break. An Instron 4302 type (manufactured by Instron) was used as a measuring instrument, and an elastomer processed into a No. 2 type test piece (JIS K 7113) was used as a test piece. The results are shown in Table 2.

[0078]

[Table 2]

As is clear from Table 2, the acrylic elastomers (1) to (6) obtained by the production method of the present invention were excellent in both moldability and mechanical properties.

However, the acrylic elastomers (1) and (2) for comparison did not flow at 160 ° C. at all, and the molding processability was extremely poor.

Example 15 After 1.2 g (0.005 mol) of zinc dimethacrylate was mixed and dissolved in 127 g (0.99 mol) of n-butyl acrylate, 0.35 g (0.0025 mol) of salicylic acid was added. Dissolved. To this polymerizable monomer mixture, 1.0 g of lauroyl peroxide as a radical polymerization initiator and 0.5 g of 1-dodecanethiol as a chain transfer agent were added and dissolved to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C for 3 hours, and then the cast resin was taken out and heated at 80 ° C for 2 hours. The pressure-sensitive adhesive of the present invention (hereinafter, referred to as pressure-sensitive adhesive (1)) was obtained.
The molecular weight of this adhesive (1) is determined by gel permeation
The weight average molecular weight (hereinafter referred to as Mw) is 200,000 and the number average molecular weight (hereinafter referred to as Mn) is 1 as measured by chromatography (8010 type manufactured by Tosoh Corporation).
It was 10,000. This adhesive (1) was uniformly applied onto a polyester film (PET, thickness 25 μm) so that the coating thickness was 25 μm, to obtain a sample tape (hereinafter referred to as sample tape (1)).

Example 16 With respect to a mixed solution of 100 g (0.78 mol) of n-butyl acrylate and 37 g (0.2 mol) of 2-ethylhexyl acrylate, the water content was 0.54 g (0.03 mol). Water was added and dissolved so that The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 1.2 g (0.01 mol) of benzoic acid and 4.7 g (0.02 mol) of zinc dimethacrylate were mixed and dissolved. To this polymerizable monomer mixture, 1.0 g of azobisisobutyronitrile as a radical polymerization initiator and 0.5 g of 1-dodecanethiol as a chain transfer agent were added and dissolved to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C for 3 hours, and then the cast resin was taken out and heated at 80 ° C for 2 hours. Then, the pressure-sensitive adhesive of the present invention (hereinafter, referred to as pressure-sensitive adhesive (2)) was obtained. The molecular weight of this adhesive (2) was determined by gel permeation chromatography (8, manufactured by Tosoh Corporation).
010 type), Mw is 190,000, Mn
Was 80,000. The pressure-sensitive adhesive (2) was uniformly applied onto a polyester film (PET, thickness 25 μm) so that the coating thickness was 25 μm to obtain a sample tape (hereinafter referred to as sample tape (2)).

Example 17 Water was added to and dissolved in 124 g (0.97 mol) of n-butyl acrylate so that the water content was 0.72 g (0.04 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Further, 3.5 g (0.03 mol) of hexanoic acid and 7.1 g (0.03 mol) of zinc dimethacrylate were mixed and dissolved. 1.0 g of benzoyl peroxide as a radical polymerization initiator and 1 as a chain transfer agent were added to this polymerizable monomer mixture.
-0.5 g of dodecanethiol was added and dissolved to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C for 3 hours, and then the cast resin was taken out and heated at 80 ° C for 2 hours. The pressure-sensitive adhesive of the present invention (hereinafter, referred to as pressure-sensitive adhesive (3)) was obtained. The molecular weight of this pressure-sensitive adhesive (3) was measured by gel permeation chromatography (8010 type manufactured by Tosoh Corporation), and Mw was 180,000 and Mn was 80,000. This adhesive (3) was uniformly applied onto a polyester film (PET, thickness 25 μm) so that the coating thickness was 25 μm, to obtain a sample tape (hereinafter, referred to as sample tape (3)).

Example 18 To a mixed liquid of 64 g (0.5 mol) of n-butyl acrylate, 66 g (0.36 mol) of 2-ethylhexyl acrylate and 8.6 g (0.1 mol) of methyl acrylate. ,
Water was added and dissolved so that the water content was 1.1 g (0.06 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Further, 4.6 g (0.04 mol) of hexanoic acid and 9.4 g (0.04 mol) of zinc dimethacrylate were mixed and dissolved. To this polymerizable monomer mixture, 1.0 g of azobisisobutyronitrile as a radical polymerization initiator and 0.5 g of 1-dodecanethiol as a chain transfer agent were added and dissolved to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C for 3 hours, and then the cast resin was taken out and heated at 80 ° C for 2 hours. The pressure-sensitive adhesive of the present invention (hereinafter, referred to as pressure-sensitive adhesive (4)) was obtained.
The molecular weight of this adhesive (4) is determined by gel permeation
Mw was 180,000 and Mn was 80,000 when measured using chromatography (Tosoh Corporation Model 8010). This adhesive (4) was applied to a polyester film (PE
(T, thickness 25 μm) to obtain a sample tape (hereinafter referred to as sample tape (4)).

Example 19 To a mixed solution of 26 g (0.2 mol) of n-butyl acrylate, 112 g (0.61 mol) of 2-ethylhexyl acrylate and 7.9 g (0.11 mol) of acrylic acid, Water was added and dissolved so that the water content was 1.3 g (0.07 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
Further, 11 g (0.08 mol) of salicylic acid and 19 g (0.08 mol) of zinc dimethacrylate were mixed and dissolved. This polymerizable monomer mixture was dissolved in 200 g of ethyl acetate. To this solution, 0.6 g of benzoyl peroxide as a radical polymerization initiator and 0.3 g of 1-dodecanethiol as a chain transfer agent were added and dissolved to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was solution polymerized at 70 ° C. for 5 hours to obtain a pressure-sensitive adhesive solution containing the pressure-sensitive adhesive of the present invention (hereinafter, this will be referred to as pressure-sensitive adhesive (5)). The solvent was volatilized from this pressure-sensitive adhesive solution to obtain a pressure-sensitive adhesive (5). The molecular weight of this pressure-sensitive adhesive (5) was measured by gel permeation chromatography (8010 type manufactured by Tosoh Corporation), and Mw was 170,000 and Mn was 70,000. This adhesive (5) was applied to polyester film (PET, thickness 25μ
m), so that the coating thickness is 25 μm.
A sample tape (hereinafter, referred to as sample tape (5)) was obtained.

Comparative Example 9 1.2 g (0.005 mol) of zinc dimethacrylate was mixed and dissolved in 127 g (0.99 mol) of n-butyl acrylate. 1.0 g of lauroyl peroxide as a radical polymerization initiator and 1- as a chain transfer agent were added to the polymerizable monomer mixture.
0.5 g of dodecanethiol was added and dissolved to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C for 3 hours, and then the cast resin was taken out and heated at 80 ° C for 2 hours. Then, a comparative pressure-sensitive adhesive (hereinafter, referred to as a comparative pressure-sensitive adhesive (1)) was obtained. The molecular weight of this pressure-sensitive adhesive for comparison (1) was determined by gel permeation chromatography (8010 manufactured by Tosoh Corporation).
Mw was 200,000 and Mn was 80,000. This comparative pressure-sensitive adhesive (1) was evenly applied onto a polyester film (PET, thickness 25 μm) so as to have a coating thickness of 25 μm, and a comparative sample tape (hereinafter referred to as comparative sample tape (1) To get).

Comparative Example 10 0.54 g (0.03 mol) of water was added to a mixed liquid of 100 g (0.78 mol) of n-butyl acrylate and 37 g (0.2 mol) of 2-ethylhexyl acrylate. Water was added and dissolved so that The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). 4.1 g of zinc diacrylate
(0.02 mol) were mixed and dissolved. To this polymerizable monomer mixture, 1.0 g of azobisisobutyronitrile as a radical polymerization initiator and 0.5 g of 1-dodecanethiol as a chain transfer agent were added and dissolved to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was poured into a cell assembled using two glass plates and a Teflon gasket,
Polymerize at 0 ° C for 3 hours and then remove the casting resin
After heating at 0 ° C. for 2 hours, a comparative pressure-sensitive adhesive (hereinafter, referred to as comparative pressure-sensitive adhesive (2)) was obtained. The molecular weight of this pressure-sensitive adhesive for comparison (2) was measured by gel permeation chromatography (Type 8010 manufactured by Tosoh Corporation), and Mw was 180,000 and Mn was 80,000. This comparative pressure-sensitive adhesive (2) was evenly applied on a polyester film (PET, thickness 25 μm) to a coating thickness of 25 μm, and a comparative sample tape (hereinafter referred to as comparative sample tape (2) To get).

Comparative Example 11 To 124 g (0.97 mol) of n-butyl acrylate, water was added and dissolved so that the water content was 0.72 g (0.04 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Furthermore, 5.5 g of calcium diacrylate (0.
03 mol) were mixed and dissolved. 1.0 g of benzoyl peroxide as a radical polymerization initiator was added to the polymerizable monomer mixture.
0.5 g of 1-dodecanethiol was added and dissolved as a chain transfer agent to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C for 3 hours, and then the cast resin was taken out and heated at 80 ° C for 2 hours. Comparative adhesive (hereinafter, referred to as Comparative adhesive (3)
I got). The molecular weight of this comparative pressure-sensitive adhesive (3) was measured by gel permeation chromatography (8010 type manufactured by Tosoh Corporation), and Mw was 1
70,000 and Mn were 70,000. This comparative pressure-sensitive adhesive (3) was evenly applied onto a polyester film (PET, thickness 25 μm) to a coating thickness of 25 μm, and a comparative sample tape (hereinafter referred to as comparative sample tape (3) Do)
I got

Comparative Example 12 To a mixed liquid of 64 g (0.5 mol) of n-butyl acrylate, 66 g (0.36 mol) of 2-ethylhexyl acrylate and 8.6 g (0.1 mol) of methyl acrylate. ,
Water was added and dissolved so that the water content was 1.1 g (0.06 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Further, 9.6 g (0.04 mol) of zinc dimethacrylate was mixed and dissolved. Azobisisobutyronitrile 1.0 was added to the polymerizable monomer mixture as a radical polymerization initiator.
g and 0.5 g of 1-dodecanethiol as a chain transfer agent were added and dissolved to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was poured into a cell assembled using two glass plates and a Teflon gasket, polymerized at 60 ° C for 3 hours, and then the cast resin was taken out and heated at 80 ° C for 2 hours. Then, a pressure-sensitive adhesive for comparison (hereinafter, referred to as a pressure-sensitive adhesive for comparison (4)) was obtained. The molecular weight of this pressure-sensitive adhesive for comparison (4) was measured by gel permeation chromatography (8010 type manufactured by Tosoh Corporation), and M was obtained.
The w was 190,000 and the Mn was 90,000. A polyester film (PET, thickness 25 μ
m), so that the coating thickness is 25 μm.
A comparative sample tape (hereinafter referred to as comparative sample tape (4)) was obtained.

Comparative Example 13 To a mixed solution of 26 g (0.2 mol) of n-butyl acrylate, 112 g (0.61 mol) of 2-ethylhexyl acrylate and 7.9 g (0.11 mol) of acrylic acid, Water was added and dissolved so that the water content was 1.3 g (0.07 mol). The amount of water was measured using a Karl Fischer moisture meter (MKS-3P type manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
Further, 19 g (0.08 mol) of zinc dimethacrylate was mixed and dissolved. This polymerizable monomer mixture was dissolved in 200 g of ethyl acetate. To this solution, 0.6 g of benzoyl peroxide as a radical polymerization initiator and 0.3 g of 1-dodecanethiol as a chain transfer agent were added and dissolved to prepare a polymerizable monomer mixture. This polymerizable monomer mixture was added at 70 ° C for 5
Solution polymerization was carried out for a period of time to obtain a pressure-sensitive adhesive solution containing a pressure-sensitive adhesive for comparison (hereinafter, this will be referred to as pressure-sensitive adhesive for comparison (5)). The solvent was volatilized from this pressure-sensitive adhesive solution to obtain a pressure-sensitive adhesive for comparison (5). The molecular weight of this comparative pressure-sensitive adhesive (5) was determined by gel permeation chromatography (80 manufactured by Tosoh Corporation).
Mw was 160,000 and Mn was 60,000 when measured using a 10 type). This comparative pressure-sensitive adhesive (5) was applied on a polyester film (PET, thickness 25 μm) with a thickness of 25 μm.
It was evenly coated so as to give m, to obtain a comparative sample tape (hereinafter referred to as comparative sample tape (5)).

Example 20 Adhesives (1) to (5) of the present invention obtained in Examples 15 to 19 and Comparative Examples 9 to 13 and adhesives for comparison (1) to
The viscosity characteristics of (5) during heating and melting were evaluated by the melt viscosity at 180 ° C. Specifically, the pressure-sensitive adhesive (1) of the present invention
After leaving (5) and the pressure-sensitive adhesives for comparison (1) to (5) at 180 ° C. for 20 minutes, the melt viscosity was evaluated at that temperature using a B-type viscometer (BM type manufactured by Tokimec Co., Ltd.).

Further, Examples 15 to 19 and Comparative Examples 9 to 1
Using the sample tapes (1) to (5) and the comparative sample tapes (1) to (5) obtained in No. 3, the pressure-sensitive adhesive (1) of the present invention
To (5) and comparative pressure-sensitive adhesives (1) to (5) were evaluated for heat resistance, cohesive force, adhesive force, and tack as follows.

The heat resistance was evaluated by the cohesive force at 80 ° C. Specifically, after attaching the sample tapes (1) to (5) and the comparative sample tapes (1) to (5) (25 mm × 25 mm) on a stainless steel plate (SUS304), one round trip of pressurization with a 2 kgf rubber roll was performed. After leaving it at 80 ℃ for 20 minutes, make the stainless plate vertical at that temperature and put 1kg on the lower end of the sample.
Was applied to evaluate the shift length after 24 hours.

The cohesive force was evaluated by the following method. Specifically, after attaching the sample tapes (1) to (5) and the comparative sample tapes (1) to (5) (25 mm × 25 mm) on a stainless steel plate (SUS304), one round trip of pressurization with a 2 kgf rubber roll was performed. After standing at 23 ° C. for 20 minutes, the stainless plate was made vertical at that temperature, a load of 1 kg was applied to the lower end of the sample, and the shift length for 24 hours was evaluated.

The adhesive strength was evaluated by the following method. Specifically, after attaching the sample tapes (1) to (5) and the comparative sample tapes (1) to (5) (25 mm × 25 mm) on a stainless steel plate (SUS304), one round trip of pressurization with a 2 kgf rubber roll was performed. After being left at 23 ° C. for 20 minutes, the peel strength when pulled in a 180 ° direction at a pulling speed of 300 mm / min in an atmosphere of 23 ° C. was evaluated.

The tack was evaluated by the following method. Specifically, the pressure-sensitive adhesive layer is placed on the inclined surface of the sample tapes (1) to (5) and the comparative sample tapes (1) to (5) with an inclination angle of 30 degrees, and 1/32 inch to 32 in diameter from 10 cm above the slope
Hard spheres with different diameters in the range of / 32 inches were rolled under a temperature atmosphere of 23 ° C. The maximum diameter of the hard sphere stationary within 10 cm below the inclined surface from the upper end of the sample tape was evaluated.
Table 3 shows the results.

[0097]

[Table 3]

As is clear from Table 3, the pressure-sensitive adhesives (1) to (5) obtained by the production method of the present invention showed almost no deviation even when subjected to a cohesive strength test at 80 ° C. for 24 hours, and had heat resistance. Was excellent. Further, the melt viscosity at 180 ° C. is 500.
It was in the range of 0 to 10000 cP and had excellent viscosity characteristics when heated and melted. Furthermore, the adhesive properties such as cohesive strength at 23 ° C., adhesive strength, and tack were all excellent.

However, the comparative pressure-sensitive adhesives (1) to (5) are 8
Even when a cohesive strength test was carried out at 0 ° C. for 24 hours, almost no deviation was observed and the heat resistance was excellent, but the melt viscosity at 180 ° C. was 30,000 cP or more, and the viscosity characteristics during heating and melting were extremely poor.

[0100]

According to the present invention, a polymerizable monomer mixture containing a polyvalent metal salt compound of an organic carboxylic acid having a polymerizable double bond (A) and a vinyl monomer (B) is used. When producing a thermoplastic resin by polymerizing, by coexisting with an organic carboxylic acid compound (C) having no polymerizable double bond and copolymerizing, heat resistance, molding processability, mechanical properties and transparency are improved. Excellent thermoplastic resin useful as a molding material, thermoplastic resin useful as an acrylic elastomer excellent in molding processability and mechanical properties, and further heat resistance, viscosity characteristics at the time of heating and melting, cohesive force at room temperature, adhesion Power,
It is possible to easily obtain a thermoplastic resin which is useful as an adhesive having excellent adhesive properties such as tack.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinobu Asako 12-25 Kannondai, Tsukuba, Ibaraki Prefecture

Claims (8)

[Claims] 1. A thermoplastic resin obtained by copolymerizing a polymerizable monomer mixture containing a polyvalent metal salt compound of an organic carboxylic acid having a polymerizable double bond (A) and a vinyl monomer (B). A method for producing a thermoplastic resin, comprising the step of producing an organic carboxylic acid compound (C) having no polymerizable double bond, and copolymerizing the same. 2. The production method according to claim 1, wherein the polyvalent metal salt compound (A) of an organic carboxylic acid having a polymerizable double bond is a polyvalent metal salt compound of (meth) acrylic acid. 3. The process according to claim 1 or 2, wherein the vinyl monomer (B) is a monomer containing at least one compound selected from the group consisting of (meth) acrylic acid ester compounds and styrene. Method. 4. A vinyl monomer (B) in an amount of 0.
The production method according to claim 1, wherein the copolymerization is carried out in the presence of water in a proportion of 005 to 0.3 mol. 5. The production method according to claim 1, wherein the vinyl monomer (B) has methyl methacrylate as a main component. 6. The vinyl monomer (B) has a glass transition temperature of −10 for a polymer obtained from the vinyl monomer (B).
The manufacturing method according to any one of claims 1 to 4, which is in a range of 0 to 20 ° C. 7. The production method according to claim 1, wherein the vinyl monomer (B) has ethyl acrylate as a main component. 8. The vinyl monomer (B) is acrylic acid n-
5. A butyl and / or 2-ethylhexyl acrylate as a main component.
Manufacturing method described in.