JP2002105127A - Reaction product containing metal salt-having vinylic monomer and polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reaction product containing a metal salt-containing vinylic monomer which contains the metal salt in a high concentration and has been produced without using a solvent. SOLUTION: This reaction product characterized by containing a metal salt-having vinylic monomer obtained by reacting a metal compound with one or more unsaturated acids selected from the group of unsaturated acids consisting of the mono[alkylene glycol (meth)acrylate] esters of phthalic acid which may have one or more substituents on the aromatic ring and whose aromatic ring may be hydrogenated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a metal salt which can be easily introduced into a polymer by (co) polymerization, cross-linking reaction or the like, and is used for the purpose of reinforcing rubber or the like. The present invention relates to a reaction product containing a vinyl monomer and a polymer using the same.

[0002]

2. Description of the Related Art Conventionally, a vinyl monomer having a metal salt used for reinforcing rubber, such as zinc (meth) acrylate, generally reacts an unsaturated acid with a metal compound. The obtained reaction product is obtained by isolating it in a powder state. That is, the vinyl monomer having the above-mentioned metal salt usually reacts with the unsaturated acid and the metal compound, removes the eliminated components such as water generated by the reaction out of the reaction system, and after washing and drying the reaction product, Since it is obtained by isolation, there is a disadvantage that the production process is complicated. A vinyl monomer having a powdered metal salt is 1) for example, when kneaded in rubber or the like and used as a cross-linking agent, it takes a long time for kneading or the cross-linking reaction becomes uneven. 2) there is a drawback in that the powder is blocked (consolidated), which hinders storage and handling.

[0003] As a method for improving the above-mentioned disadvantages of the powder, for example, Japanese Patent Publication No. 1-60491 and Japanese Patent Application Laid-Open No.
704, JP-A-9-104845, JP-A-10-245421 and JP-A-10-2454
No. 22 discloses a method in which a reaction product containing a vinyl monomer having a metal salt obtained by reacting an unsaturated acid with a metal compound in a solvent is used for (co) polymerization.

[0004]

However, in the above-mentioned conventional method, the solvent imposes a negative restriction on the selection of the finally obtained copolymer composition or crosslinked product composition, and causes a problem of odor during handling. There are problems such as becoming. The above problem cannot be solved by using a copolymerizable vinyl monomer as the solvent.

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a liquid reaction product excellent in handleability and containing substantially only a vinyl monomer having a metal salt. It is in. Another object of the present invention is to
Chemical resistance and water resistance, such as alkali resistance, mechanical strength such as tensile strength and tear strength, hardness, dynamic viscosity obtained by (co) polymerizing the polymerizable composition containing the above reaction product. Elasticity, abrasion resistance, bending fatigue resistance, heat generation, toughness,
To provide a polymer (excellent in heat resistance, oil resistance, weather resistance, transparency, etc., excellent in retention of hardness and rebound, etc., and low in creep such as compression set and tensile elongation (low creep). It is in.

[0006]

Means for Solving the Problems In order to achieve the above object, the present inventors have intensively studied a stable reaction product containing a vinyl monomer having a metal salt. As a result, for example, by reacting a metal compound with one or more unsaturated acids selected from the group of specific unsaturated acids such as acrylate-modified monomers of ethylene glycol monophthalate, substantially without using a solvent. The present inventors have found that a reaction product containing a vinyl monomer having a metal salt can be produced in a simple process with good productivity and at low cost, and have completed the present invention.

That is, in order to solve the above-mentioned problems, the reaction product according to the present invention may have a substituent on an aromatic ring, and may further contain a mono-phthalic acid whose aromatic ring may be hydrogenated. Vinyl monomer having a metal salt obtained by reacting one or more unsaturated acids selected from the group of unsaturated acids that are (alkylene glycol (meth) acrylate) esters with a metal compound substantially without using a solvent. It is characterized by including.

[0008] In order to solve the above-mentioned problems, the reaction product according to the present invention is characterized in that the one or more unsaturated acids are represented by the general formula (1) or the general formula (2).

[0009]

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(Wherein R ₁ is a hydrogen atom or a group having 1 to 1 carbon atoms)
4 represents an alkyl group, R ₂ represents an alkylene group having 2 to 4 carbon atoms, R ₃ represents a substituent other than a hydrogen atom, n represents an integer of 1 to 8, and m represents an integer of 0 to 4. Which is selected from the group of unsaturated acids represented by:

The reaction product according to the present invention is characterized in that the above-mentioned reaction is carried out in a plastic substance in order to solve the above-mentioned problems.

In order to solve the above-mentioned problems, the polymer according to the present invention is characterized in that a polymerizable composition containing the above reaction product is (co) polymerized.

According to the above construction, the aromatic ring may have a substituent, and the aromatic ring may be hydrogenated.
By using one or more unsaturated acids selected from the group of unsaturated acids which are acrylates) esters, a stable and transparent liquid reaction containing a vinyl monomer having a metal salt can be produced without using a solvent substantially. You can get things.

This eliminates the need for a complicated process for isolating the vinyl monomer having a metal salt, thereby simplifying the process for producing a reaction product containing the vinyl monomer having a metal salt. Further, since the above reaction product is produced substantially without using a solvent, the copolymer composition or the crosslinked product composition of the polymer obtained by (co) polymerizing the polymerizable composition containing the reaction product is obtained. There is no negative constraint on the choice. In addition, there is no problem that odor of the solvent occurs during handling. In the present invention, “substantially no solvent is used” means that the solvent in the reaction system (unsaturated acid, metal compound and reaction product) is 10%.
% Or less, more preferably 5% by weight or less, still more preferably 3% by weight or less, and most preferably 0% by weight. Further, in the present invention, the "polymerizable composition" refers to a reaction product itself obtained by reacting an unsaturated acid and a metal compound substantially without using a solvent, or the reaction product and a vinyl monomer A mixture with a (co) polymerizable substance such as a body.

Since the above reaction product is produced without using a solvent, it is substantially composed of a vinyl monomer having a metal salt. Therefore, the metal salt can be more stably introduced into the resin skeleton of the polymer obtained by (co) polymerizing the polymerizable composition containing the reaction product than before. That is, the degree of ionic crosslinking of the polymer obtained by (co) polymerizing the polymerizable composition can be sufficiently increased. Therefore, mechanical strength such as tensile strength and tear strength, hardness, dynamic viscoelasticity, abrasion resistance, bending fatigue resistance, heat generation, toughness, heat resistance, oil resistance,
It is possible to produce a polymer (excellent in various properties such as weather resistance and transparency, retention of hardness and repulsion, etc.) and low in creep (low creep) such as compression set and tensile elongation. In addition, when the polymerizable composition contains a polyfunctional vinyl monomer, the balance between the mechanical strength and various physical properties such as creep of the polymer can be particularly improved.

Further, according to the above configuration, the reaction product is converted from the raw material for forming the reaction product to a so-called 1 pot.
(One pot). Therefore,
A reaction product containing a vinyl monomer having a metal salt can be produced in a simple process with good productivity and at low cost. In the case where a polymer is produced by (co) polymerizing the polymerizable composition containing the above reaction product, a post-crosslinking step is not required, so that a polymer having a crosslinked structure can be produced in a simple step with good productivity. , And can be manufactured at low cost.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The reaction product according to the present invention may have a substituent on the aromatic ring, and further may be an unsaturated acid which is a mono (alkylene glycol (meth) acrylate) ester of phthalic acid in which the aromatic ring may be hydrogenated. And a mixture of two or more unsaturated acids selected from the group consisting of a vinyl monomer having a metal salt obtained by reacting a metal compound with a solvent, and more specifically, a general formula (1) or general formula (2)

[0018]

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(Wherein R ₁ is a hydrogen atom or a group having 1 to 1 carbon atoms)
4 represents an alkyl group, R ₂ represents an alkylene group having 2 to 4 carbon atoms, R ₃ represents a substituent other than a hydrogen atom, n represents an integer of 1 to 8, and m represents an integer of 0 to 4. Represents one or more unsaturated acids selected from the group of unsaturated acids represented by
It is produced by reacting with a metal compound substantially without using a solvent.

Among the unsaturated acids represented by the above general formula (1) or (2), the unsaturated acid wherein the (alkylene glycol (meth) acrylate) ester substituent is located ortho to the carboxy group. General formula (3) or general formula (4)

[0021]

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(Wherein R ₁ is a hydrogen atom or a group having 1 to 1 carbon atoms)
4 represents an alkyl group, R ₂ represents an alkylene group having 2 to 4 carbon atoms, R ₃ represents a substituent other than a hydrogen atom, n represents an integer of 1 to 8, and m represents an integer of 0 to 4. Is more preferable.

Further, among the unsaturated acids represented by the above general formula (3) or (4), R ₃ which is a substituent other than a hydrogen atom is a halogen and the number of substitution m is 4 Certain unsaturated acids are particularly preferred. Examples of the halogen include bromine, chlorine, and fluorine.

The unsaturated acid represented by the general formula (1), (2), (3) or (4) according to the present invention may be, for example, a compound represented by the formula (a) Mono (ethylene glycol) phthalate acrylate represented by formula (b), mono (propylene glycol) represented by formula (b)
Monophthalate alkylene glycol acrylates such as phthalate acrylate, mono (diethylene glycol) phthalate acrylate represented by formula (c), and mono (dipropylene glycol) phthalate acrylate represented by formula (d); represented by formula (e) Mono (ethylene glycol) phthalate methacrylate, formula (f)
Mono (propylene glycol) phthalate methacrylate represented by formula (g), mono (diethylene glycol) phthalate methacrylate represented by formula (g), mono (phthalic acid) alkylene glycol methacrylate such as mono (dipropylene glycol) phthalate methacrylate represented by formula (h) Mono (halogen-substituted phthalate alkylene glycol) methacrylates such as mono (ethylene glycol) tetrachlorophthalate methacrylate represented by formula (i) and mono (ethylene glycol) tetrabromophthalate methacrylate represented by formula (j);
And unsaturated acids in which the benzene nucleus (benzene ring) in these compounds is hydrogenated; and the like, but is not particularly limited thereto. These compounds may be used alone or in combination of two or more.

[0025]

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As the unsaturated acid in the present invention, at least one selected from the group consisting of unsaturated acids represented by the general formulas (1), (2), (3) and (4) Unsaturated acids are used. When a mixture of two or more unsaturated acids is used as the unsaturated acid, the proportion of one type of unsaturated acid in the mixture of unsaturated acids is preferably in the range of 10 to 90 mol%, more preferably 20 to 80 mol%. % Is more preferable.
By setting the proportion of one kind of unsaturated acid within the above range, the vinyl monomer having a metal salt obtained by reacting the unsaturated acid with the metal compound can be dissolved in other (co) polymerizable substances or solvents. Sex will be further improved.

The above unsaturated acid may further contain a vinyl monomer having a carboxyl group (hereinafter referred to as vinyl monomer A). However, when the unsaturated acid further contains a vinyl monomer A, the amount of the vinyl monomer A is preferably less than 30 mol%, more preferably less than 20 mol%, based on the total unsaturated acid. When the vinyl monomer A is used in an amount of 30 mol% or more based on the total unsaturated acid, it is difficult to obtain a uniform liquid reaction product which is the object of the present invention. In the present invention, the monomer A does not include the unsaturated acid represented by the general formula (1) or (2).

As the vinyl monomer A, for example,
Α, β-ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; esters having an ester group, such as 2-methacryloyloxyethyl trimellitic acid and 2-methacryloyloxyethyl pyromellitic acid; Saturated carboxylic acids; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; monoesters of unsaturated dicarboxylic acids and monohydric alcohols such as maleic acid monomethyl ester; These compounds may be used alone or in combination of two or more, if necessary.

Examples of the metal compound in the present invention include inorganic metal compounds such as metal oxides, metal hydroxides, metal chlorides and metal carbonates; metal carboxylate salts such as metal acetate salts; and complexes such as acetylacetone complexes. Organic metal compounds such as metal alcoholates such as metal propylate and metal butyrate; and the like, but are not particularly limited. These compounds may be used alone or in combination of two or more, if necessary. In addition,
The above metal may be a monovalent metal or a polyvalent metal.

Among the above metal compounds, metal oxides and metal hydroxides are more preferable, and polyvalent metal oxides and polyvalent metal hydroxides are more excellent in reactivity with unsaturated acids. Therefore, it is more preferable. Specific examples of the polyvalent metal oxide include zinc oxide (zinc white) and magnesium oxide, but are not particularly limited. As the polyvalent metal hydroxide, specifically,
For example, zinc hydroxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide and the like can be mentioned, but it is not particularly limited. Among the metal compounds exemplified above,
Zinc oxide and zinc hydroxide are particularly preferred.

Although the reaction product according to the present invention does not substantially contain a solvent, it may be used by adding a solvent (solvent) if necessary. In this case, it is more preferable to use a reaction product obtained by using a mixture of two or more unsaturated acids. A vinyl monomer having a metal salt obtained by reacting a mixture of two or more unsaturated acids with a metal compound has good solubility in a solvent, so that the transparency of the mixture of the reaction product and the solvent is more excellent. Become.

In the reaction between the unsaturated acid and the metal compound,
The equivalent ratio of the two (unsaturated acid / metal compound) is set according to the composition of the unsaturated acid, the type of the metal compound, the combination of the two, the use of the reaction product, and various physical properties required for the reaction product. It suffices if there is no particular limitation.
The range of 0 to 1.2 is more preferable.

The method of reacting the unsaturated acid with the metal compound is not particularly limited. Specifically, for example, after mixing the unsaturated acid with the metal compound, the mixture is stirred at room temperature or under heating. Method. Thereby, the reaction between the two proceeds, and a vinyl monomer having a metal salt is formed. The method of mixing the unsaturated acid and the metal compound is not particularly limited, and for example, a method of adding a metal compound to an unsaturated acid and mixing; a method of adding an unsaturated acid to a metal compound and mixing; A method of simultaneously mixing a saturated acid and a metal compound; and the like.

Whether the reaction between the unsaturated acid and the metal compound is completed is determined, for example, by determining whether the reaction system is uniform and transparent at room temperature when the metal compound used is insoluble in the reaction system. You can check with The point at which a reaction product that is uniform and transparent at room temperature is obtained is the end point of the above reaction. Therefore, the operation such as stirring may be terminated at the above time. The reaction conditions such as the reaction temperature and the reaction time may be any conditions as long as the above-mentioned reaction proceeds and the substances (unsaturated acids, metal compounds and reaction products) of the reaction system are not altered. is not.

In the above reaction, in order to avoid polymerization of the unsaturated acid during the reaction, for example, a polymerization inhibitor such as hydroquinone is added to the reaction system, or the reaction is carried out in an air / nitrogen mixed gas atmosphere. You can also go below.

The reaction between the unsaturated acid and the metal compound in the present invention is carried out in advance in the next step when the reaction product is used by dispersing or dissolving the reaction product in a plastic such as rubber. May be. In the present invention, the term “plastic substance” refers to a substance that is fluid at normal temperature or under heating. Examples of the above-mentioned plastic material include unvulcanized rubber or liquid rubber such as unvulcanized butadiene rubber, unvulcanized hydrogenated nitrile butadiene rubber and liquid nitrile butadiene rubber; plasticizers such as dioctyl phthalate; soft vinyl chloride and plastisol Plasticizers containing plasticizers such as, for example; softeners such as highly aromatic oils and naphthenic oils; unsaturated polyesters, vinyl ester resins,
Thermosetting prepolymers such as urethane acrylate; and the like, but are not particularly limited. These plastic substances may be used alone or in combination of two or more. The compounding ratio of the reaction product and the plastic substance may be set according to the type of the reaction product and the composition of the plastic substance, a combination of the two, the use of the plastic substance and various required physical properties, and is particularly limited. Not something.

Since the reaction product according to the present invention uses an unsaturated acid having a specific skeleton as a raw material, it contains a vinyl monomer having a high concentration of a metal salt and can be formed into a uniform and stable liquid. it can. Therefore, the reaction product can be widely used for (co) polymerization, crosslinking reaction and the like. That is, by (co) polymerizing the polymerizable composition containing the above reaction product, a metal salt group can be efficiently introduced at an arbitrary concentration into the obtained polymer skeleton. Therefore, the degree of ionic crosslinking of the polymer can be sufficiently increased. Therefore, mechanical strength such as tensile strength and tear strength, hardness, dynamic viscoelasticity, abrasion resistance, bending fatigue resistance, heat generation, toughness, heat resistance, oil resistance,
A polymer having excellent properties such as weather resistance and transparency, excellent hardness and rebound resilience, and low creep such as compression set and tensile elongation (low creep) can be produced. That is, as a result of introducing a metal salt group into a polymer using the polymerizable composition containing the above reaction product, the physical properties of the polymer are improved.

The reaction products according to the invention do not require a solubilizing agent. Therefore, the polymer obtained by (co) polymerizing the polymerizable composition containing the reaction product does not cause a decrease in performance due to the solubilizing agent. Therefore, the polymer has improved chemical resistance such as alkali resistance and water resistance as compared with a polymer using a conventional solubilizer. That is, as a result of introducing a group of a metal salt into a polymer using the polymerizable composition containing the above reaction product, the chemical properties of the polymer are improved.

Since the polymerizable composition according to the present invention contains substantially no solvent, there is little restriction on the composition of the polymer obtained by (co) polymerizing the polymerizable composition, and the odor due to the solvent is reduced. Excellent in that there are no problems.

The method for (co) polymerizing the polymerizable composition according to the present invention into a polymer is not particularly limited. Examples of the above method include a polymerization method by heating; a polymerization method of irradiating ultraviolet rays or radiation such as an electron beam;
A polymerization method using a polymerization initiator such as a radical polymerization initiator;
And various other known polymerization methods. As the form of the polymerization reaction, various known reaction forms such as bulk polymerization, suspension polymerization, emulsion polymerization, and dispersion polymerization can be adopted. Therefore, the obtained polymer can be obtained in various shapes such as a sheet shape, a granular shape (bead shape), a powdery shape, and a fine particle shape, depending on the form of the polymerization reaction.
Among these, the method of adding a radical polymerization initiator to the polymerizable composition containing the reaction product and performing bulk polymerization is the most preferable because the production process is the simplest and the polymer can be produced at low cost. .

Specific examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide and t-amyl peroxy-2-ethylhexanoate; Organic azo compounds such as azobisisobutyronitrile; benzophenone, acetophenones, and acylphosphine oxide; The amount of the radical polymerization initiator added is
There is no particular limitation. Further, a polymerization accelerator may be used in combination with the radical polymerization initiator. Specific examples of the polymerization accelerator include organic metal salts such as cobalt octenoate and zinc stearate; aromatic tertiary amines such as dimethylaniline; and triphenylphosphine. Furthermore, polymerization regulators (so-called polymerization inhibitors)
And a photosensitizer may be used in combination with the radical polymerization initiator. Specific examples of the polymerization regulator include benzoquinone, paramethoxyphenol, hydroquinone and the like. In the case where a polymerization accelerator, a polymerization regulator, a photosensitizer, and the like are used, their addition amounts are not particularly limited.

The reaction conditions such as the reaction pressure, the reaction temperature, and the reaction time in the above polymerization reaction are set so as to complete the polymerization reaction, for example, the composition of a reaction product or a polymerizable composition; a polymerization method; It may be appropriately set depending on the form; presence or absence of additives; and the like, and is not particularly limited. Further, the average molecular weight of the obtained polymer is not particularly limited.

When a mixture of a reaction product and a (co) polymerizable substance is used as the polymerizable composition according to the present invention,
Examples of the (co) polymerizable substance include various monofunctional vinyl monomers such as (meth) acrylate, styrene, acrylonitrile, and vinyl acetate; divinylbenzene,
Polyfunctional vinyl monomers such as ethylene glycol di (meth) acrylate, chloroprene, isoprene, butadiene, and trimethylolpropane tri (meth) acrylate; polyolefin rubbers such as nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, and liquid nitrile butadiene rubber; Thermosetting resins such as polyester, polyester acrylate, epoxy-modified vinyl ester resin and urethane acrylate; polymer syrups such as (meth) acrylate syrup of polymethyl methacrylate and (meth) acrylate syrup of side chain double bond type polybutyl methacrylate; And the like, but are not particularly limited. These compounds may be used alone or in combination of two or more.

Further, the reaction product containing the metal salt vinyl monomer having a specific structure of the present invention can be diluted with various radical polymerizable monomers as necessary to form a polymerizable composition. The amount of the metal salt vinyl monomer, that is, the amount of the reaction product of the present invention can be appropriately determined according to the required salt concentration depending on the required physical properties, and is not particularly limited.

For example, assuming that the polymerizable composition obtained by the present invention is 100% by weight, the amount of reaction produced in the polymerizable composition is in the range of 0.1 to 100% by weight, more preferably. 0.5-100% by weight, more preferably 1-100% by weight, most preferably 5-5% by weight.
In the range of 100% by weight.

The polymer (copolymer) obtained by (co) polymerizing the polymerizable composition according to the present invention can be applied to a wide range of uses. For example, by vulcanizing a polymerizable composition obtained by blending a reaction product with an unvulcanized rubber with peroxide or the like, a vulcanized rubber excellent in hardness, strength, toughness and the like can be produced. The above crosslinked rubber is used for tires,
It can be widely used for high-strength rubber, golf balls, heat-resistant rubber and the like. Further, by curing the polymerizable composition obtained by blending the reaction product with a thermosetting resin or a polymer syrup as a thermosetting compound such as a sheet molding compound (SMC) or a bulk molding compound (BMC), the hardness, A molded article excellent in strength and the like can be manufactured. By forming a polymerizable composition comprising a reaction product and a (meth) acrylate ester into a continuous sheet or the like, a tough metal crosslinked elastomer can be produced in a one-pot process. The metal crosslinked elastomer can be used for a waterproof sheet or the like. Further, by polymerizing a polymerizable composition comprising a reaction product and an alkyl acrylate such as n-butyl acrylate with heat or radiation, heat resistance and cohesive strength, adhesive strength, and excellent adhesive properties such as tackiness. An adhesive can be manufactured. The pressure-sensitive adhesive can be used for pressure-sensitive adhesive tapes, labels, sheets, and the like in a one-pot process. In addition, by mass-polymerizing a polymerizable composition comprising the above reaction product and an alkyl acrylate, as in the case of polymerization by heat or radiation, a hot-melt pressure-sensitive adhesive excellent in various physical properties is produced. be able to. Further, an emulsion obtained by emulsion polymerization of a polymerizable composition comprising a reaction product, styrene, (meth) acrylate, and the like is used as an antifouling paint,
It can be used as functional paints such as vibration damping paints and UV curable paints. Further, other uses of the polymer obtained by (co) polymerizing the polymerizable composition include, for example, an adhesive, a sealant, a thermosetting resin compound, and an asphalt modifier.

[0047]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The “parts” described in the examples indicate “parts by weight”.

The amount of the metal-containing vinyl monomer produced in the reaction product was measured by precisely weighing about 1 g of a sample in an aluminum dish having a diameter of 5 cm, diluting with acetone, air-drying, and heating in an oven at 100 ° C. for 30 minutes. The nonvolatile content after heating was determined by weighing.

Example 1 First, an unsaturated acid was synthesized by the following method. Phthalic anhydride 29 was added to a 1-L reactor equipped with a stirrer, a cooling pipe, a thermometer, and a gas introduction pipe.
6.2 parts, 2-hydroxypropyl methacrylate 30
2.8 parts, benzyltriethylammonium chloride 1.80 parts, and methylethylhydroquinone 0.0
Six parts were charged and dissolved, and heated and stirred at 105 ° C. for 9 hours under a mixed gas (the molar ratio of nitrogen to air was 2: 1). The acid value of the obtained product was 190.6 mgKOH /
g and viscosity were 6.0 Pa · s (25 ° C.). Comparison of the measured acid value and the theoretical acid value (187 mgKOH / g) confirmed that mono (propylene glycol) phthalate methacrylate was obtained as an unsaturated acid in a yield of 98%. Thus, an unsaturated acid (hereinafter, referred to as unsaturated acid (1)) was obtained.

Next, a vinyl monomer having a metal salt was synthesized. As a unsaturated acid, 155.5 parts of the above unsaturated acid (1) and mono (ethylene glycol) phthalate methacrylate were placed in a 1-L reactor equipped with a stirrer, a cooling pipe, a thermometer, and a gas introduction pipe. (Shin-Nakamura Chemical Co., Ltd .;
A mixture of 148.2 parts (the molar ratio of unsaturated acid (1) and mono (ethylene glycol) phthalate methacrylate is 1: 1) with zinc oxide (metal compound) Two kinds of zinc flowers manufactured by Sakai Chemical Co., Ltd.)
40.1 parts were added to the reactor. The molar ratio between the zinc oxide and the mixture of the two unsaturated acids was 1.0: 2.1.

Next, the contents of the reactor were heated and stirred at 70 ° C. for 8 hours under a mixed gas stream. The obtained reaction product (hereinafter, referred to as reaction product (1)) was uniform and transparent, and maintained a uniform and transparent state even after cooling to room temperature. The viscosity of the reaction product (1) is 11P
a · s (60 ° C.). Further, the reaction product (1) was uniform and transparent even after being left at room temperature for three months, and maintained the initial state. From this, it was confirmed that the total amount of the added zinc oxide was converted to the zinc salt of the two unsaturated acids. The amount of vinyl monomer having a metal salt in the reaction product (1) was 3%.
33 parts (97.0% by weight, theoretical value 94.4% by weight). Table 1 shows the results.

FIG. 1 shows an infrared ray of a mixture of unsaturated acid (1) and mono (ethylene glycol) phthalate methacrylate (the molar ratio of unsaturated acid (1) to mono (ethylene glycol) phthalate methacrylate is 1: 1). FIG. 2 shows a spectrum (IR spectrum), and FIG. 2 shows an infrared spectrum of a vinyl monomer having a metal salt contained in the reaction product (1). As is clear from the comparison between the two figures, in the infrared spectrum of FIG. 2, a strong absorption based on asymmetric stretching vibration specific to the metal carboxylate group was observed at 1573-1633 cm ⁻¹ , and the carboxyl group of the unsaturated acid was It was confirmed that it had become a zinc salt.

Example 2 In the synthesis of the vinyl monomer having a metal salt of Example 1, 155.5 parts of the unsaturated acid (1) were added to 311 parts without using mono (ethylene glycol) phthalate methacrylate. Except that the molar ratio of the saturated acid (1) and mono (ethylene glycol) phthalate methacrylate was changed to 1: 0), the same reaction and operation as in Example 1 were carried out, and the vinyl monomer having the metal salt according to the present invention was obtained. (Hereinafter referred to as reaction product (2)
To be described). The obtained reaction product (2) was uniform and transparent, and maintained a uniform and transparent state even after cooling to room temperature. The viscosity of the reaction product (2) is 1
It was 5 Pa · s (60 ° C.). Further, the reaction product (2) was uniform and transparent even after being left at room temperature for 3 months, and maintained the initial state. From this, it was confirmed that the total amount of the added zinc oxide was converted to the above-mentioned zinc salt of the unsaturated acid. The amount of vinyl monomer having a metal salt in the reaction product (2) is 33
5 parts (95.5% by weight, theoretical 94.4% by weight). Table 1 shows the results.

Example 3 In the synthesis of the vinyl monomer having a metal salt of Example 1, mono (propylene glycol) phthalate acrylate was used as an unsaturated acid (manufactured by Shin-Nakamura Chemical Co., Ltd .; trade name "NK Ester ACB200"). 2
A reaction product containing a vinyl monomer having a metal salt according to the present invention (hereinafter, referred to as reaction product (3)) is obtained by performing the same reaction and operation as in Example 1 except that only 96.4 parts is used. I got The reaction product (3) was uniform and transparent, and maintained a uniform and transparent state even after cooling to room temperature. The viscosity of the reaction product (3) is 12 Pa · s
(60 ° C.). Furthermore, the reaction product (3) was uniform and transparent even after being left at room temperature for 3 months, and maintained the initial state. From this, it was confirmed that the total amount of the added zinc oxide was converted to the above-mentioned zinc salt of the unsaturated acid. The amount of the vinyl monomer having a metal salt in the reaction product (3) was 323 parts (96.
0% by weight, theoretical 94.4% by weight). Table 1 shows the results.

Example 4 In the synthesis of the vinyl monomer having a metal salt of Example 1, NBR was used as a plastic.
Liquid rubber (acrylonitrile / butadiene copolymer liquid rubber, manufactured by Nippon Zeon Co., Ltd .; trade name "Nipol 131"
2 ") A reaction product containing a vinyl monomer having a metal salt according to the present invention (hereinafter, referred to as a reaction product (4)) by performing the same reaction and operation as in Example 3 except that 106 parts are used. I got In addition, the appearance of the used NBR liquid rubber had the same slight haze at both room temperature and 70 ° C. The appearance of the resulting reaction product (4) was uniform and slightly hazy, and maintained a uniform and slightly hazy state even after cooling to room temperature. The cloudiness of the reaction product (4) was comparable to that of the NBR liquid rubber. The viscosity of the reaction product (4) is 9.0P
a · s (55 ° C.). Furthermore, the reaction product (4)
Had a uniform and slight haze even after being left at room temperature for three months, and maintained its initial state. From this, it was confirmed that the total amount of the added zinc oxide was converted to the zinc salt of the two unsaturated acids. As a result of measuring the nonvolatile content of the NBR liquid rubber by the same method as the above-mentioned method for measuring the amount of the vinyl monomer having a metal salt in the reaction product, the result was 98.5% by weight, and the reaction product (4) The nonvolatile content therein was 96.8% by weight. From this,
The produced amount of the vinyl monomer having a metal salt in the reaction product (4) was 327 parts (72.7% by weight, theoretical value 72.1% by weight). Table 1 shows the results.

Example 5 A polymerizable composition was prepared using the reaction product (1) obtained in Example 1, and polymerized to obtain a polymer (crosslinked rubber). That is, 30 parts of the above reaction product (1) and polybutadiene rubber as unvulcanized rubber (Polybutadiene rubber with low cis content, manufactured by Nippon Zeon Co., Ltd .; trade name “Nipol BR 1241”) 1
00 parts and 1 part of dicumyl peroxide (manufactured by NOF CORPORATION; trade name “Park Mill D”) as a polymerization initiator are dissolved and mixed in cyclohexane, and the mixture is mixed with 80 parts on a glass plate.
Dried at ° C. This was transferred to a hot press and 150
Press crosslinking was performed for 1 hour at 9.81 MPa at a temperature of 9.degree. C. to obtain a crosslinked rubber sheet.

When the physical properties of the crosslinked rubber sheet thus obtained were evaluated in accordance with JIS K6301, the hardness was 90 Shore A, the tensile strength was 44 Mpa, and the elongation was 530.
%, And the rebound resilience was 55%.

Example 6 Using the reaction product (1) obtained in Example 1, a polymerizable composition was prepared and polymerized to obtain a polymer. That is, the above reaction product (1) 2.
3 parts and 97.7 parts of n-butyl acrylate are mixed to form a polymerizable composition, and a peroxide compound as a radical polymerization initiator (manufactured by Kayaku Akzo Co., Ltd .; trade name “Curing Agent 328E”) ) 1.0 part and 0.5 part of a mineral spirit solution of cobalt octenoate (cobalt content 8% by weight) as a polymerization accelerator were added and mixed. Then, the obtained mixture was injected into a cell composed of a 0.5 mm thick silicone spacer and a glass plate / release paper,
After polymerization at 0 ° C. for 90 minutes, polymerization was further performed at 160 ° C. for 30 minutes. The obtained polymer (pressure-sensitive adhesive sheet) had a ball tack (J-DOW method) of 30 and was excellent in tackiness and excellent in tear strength.

[0059]

[Table 1]

Table 1 shows examples of the synthesis of a reaction product containing a vinyl monomer having a metal salt according to the present invention, and the polymerizable composition prepared using the reaction product.
The polymer obtained by polymerization is summarized. From the results of Examples 1 to 6 shown in Table 1, without using a solvent,
A reaction product containing a vinyl monomer having a metal salt is obtained, and a polymer such as a crosslinked rubber or a pressure-sensitive adhesive sheet is obtained by (co) polymerizing a polymerizable composition prepared using the reaction product. understood.

As described above, the reaction product according to the present invention can be easily converted into a liquid reaction product containing a vinyl monomer having a high concentration of a metal salt having a good appearance without using a solvent. Obtainable. The reaction product according to the present invention has a low-cost raw material and a simple production process. Further, since the reaction product is obtained in a liquid state, it is easy to handle, and there is no need to isolate a vinyl monomer having a metal salt from the reaction product. Therefore, the reaction product according to the present invention can be widely used for various uses. Further, by polymerizing (polymerizing) the polymerizable composition containing the reaction product according to the present invention, it is possible to easily obtain a metal salt-containing polymer excellent in various physical properties at 1 pot.

[0062]

As described above, the reaction product of the present invention is:
The aromatic ring may have a substituent, and the aromatic ring may be hydrogenated. The phthalic acid may be hydrogenated mono (alkylene glycol (meth) acrylate) ester. The composition includes a vinyl monomer having a metal salt obtained by reacting a saturated acid with a metal compound substantially without using a solvent. As described above, the reaction product of the present invention has a structure in which the one or more unsaturated compounds are selected from the group of unsaturated acids represented by the general formula (1) or (2). As described above, the reaction product of the present invention has a configuration in which the above reaction is performed in a plastic substance.

As described above, the polymer of the present invention has a constitution obtained by (co) polymerizing the polymerizable composition containing the reaction product of the present invention.

As a result, there is an effect that a liquid stable reaction product containing a vinyl monomer having a high concentration of a metal salt can be provided substantially without using a solvent. In addition, since a reaction product containing a vinyl monomer having a high concentration of a metal salt can be obtained without using a solvent, the composition restriction due to the solvent is restricted by (co) polymerizing the polymerizable composition containing the reaction product. No, chemical resistance such as alkali resistance and water resistance, mechanical strength such as tensile strength and tear strength, hardness, dynamic viscoelasticity, abrasion resistance, bending fatigue resistance, heat generation, toughness, heat resistance That contains various (low creep) metal salts with low creep such as compression set and tensile elongation, as well as excellent physical properties such as heat resistance, oil resistance, weather resistance, and transparency, and retention of hardness and rebound. Is provided. Further, since no solvent is used in the reaction, there is an effect that odor due to the solvent does not occur. Further, there is an effect that a reaction product containing a vinyl monomer having the metal salt and a polymer containing the metal salt can be produced in a simple process with good productivity and at low cost.

[Brief description of the drawings]

FIG. 1 is a view showing an infrared spectrum of a mixture (a molar ratio of 1: 1) of an unsaturated acid (1) and mono (ethylene glycol) phthalate methacrylate obtained in Example 1.

FIG. 2 is a view showing an infrared spectrum of a vinyl monomer having a metal salt contained in a reaction product (1) obtained in Example 1.

Claims (4)

[Claims] 1. An unsaturated ring which may have a substituent on the aromatic ring, and which is a mono (alkylene glycol (meth) acrylate) ester of phthalic acid in which the aromatic ring may be hydrogenated. A reaction product comprising a vinyl monomer having a metal salt obtained by reacting one or more unsaturated acids with a metal compound substantially without using a solvent. 2. The method according to claim 1, wherein the at least one unsaturated acid has the general formula (1)
Or the general formula (2) (Wherein, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ represents an alkylene group having 2 to 4 carbon atoms,
R ₃ represents a substituent other than a hydrogen atom, n represents an integer of 1 to 8, and m represents an integer of 0 to 4). Item 10. The reaction product according to Item 1. 3. The reaction product according to claim 1, wherein the reaction is carried out in a plastic material. 4. A polymer obtained by (co) polymerizing a polymerizable composition containing the reaction product according to claim 1, 2 or 3.