JP2002105135A - 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 relatively high concentration and has been produced without using a solubilizing agent. SOLUTION: This reaction product characterized by containing a metal salt-having vinylic monomer obtained by reacting in a solvent a metal compound with a mixture of two 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. The solvent is preferably a vinylic monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reaction product containing a vinyl monomer having a metal salt capable of easily introducing a metal salt group into a polymer by (co) polymerization, crosslinking reaction, etc. It relates to the polymer used.

[0002]

2. Description of the Related Art Conventionally, a vinyl monomer having a metal salt typified by, for example, zinc (meth) acrylate is generally prepared by reacting an unsaturated acid with a metal compound in the form of a powder. Obtained by isolation. 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. Then, the vinyl monomer having a powdered metal salt is 1) For example, when kneaded into rubber or the like and used as a crosslinking agent,
There is a drawback that kneading takes a long time or that the crosslinking reaction becomes non-uniform; and 2) blocking (consolidation) of the powder causes trouble in handling.

Therefore, as a method of improving the above-mentioned disadvantages of the powder, there is a method in which a vinyl monomer having a metal salt of the powder is dissolved in a solvent such as a vinyl monomer and used in a solution state. However, in general, a vinyl monomer having a powdered metal salt has poor solubility in a solvent that is not miscible with water. Therefore, in order to improve the solubility of the vinyl monomer having a metal salt, a Lewis base such as an organic amine, a sulfur compound, or water is used as a solubilizing agent, and a relatively large amount of the vinyl monomer having a metal salt is used in a solvent. Has been carried out. However, when the above method is used, 1) the performance (various physical properties) of a polymer obtained by (co) polymerizing a vinyl monomer having a metal salt is reduced by the solubilizer;
2) There is a problem that it is difficult to obtain a vinyl monomer solution having a high concentration of a metal salt even if a solubilizing agent is added.

[0004] In order to solve the above problems, a method of utilizing a reaction product containing a vinyl monomer having a metal salt obtained by reacting an unsaturated acid with a metal compound in a solvent for (co) polymerization. Have been proposed. As a method of reacting an unsaturated acid and a metal compound in a solvent, for example,
Japanese Patent Publication No. 1-60491 discloses a method of using an organic metal compound such as a metal alcoholate having high reactivity as a metal compound. The method is advantageous for the industrial production of synthetic resins, since the ionic network-linked acrylic resin can be produced in one operation step from the reaction product by bulk polymerization. However, there are problems such as that organic slices of the metal alcoholate remain and that the metal alcoholate used as a raw material is expensive.

As a method for improving the above-mentioned problems, for example, Japanese Patent Application Laid-Open Nos. 9-104704 and 9-104
JP-A-845, JP-A-10-245421 and JP-A-10-245422 disclose methods of using inexpensive metal oxides and / or metal hydroxides as metal compounds.

[0006]

However, even in a method using an inexpensive metal oxide and / or metal hydroxide as a metal compound, it is necessary to obtain a stable solution containing a vinyl monomer having a high concentration of a metal salt. Requires a certain amount of the above-mentioned solubilizer. Therefore, there is a problem that the use of the solubilizing agent causes a decrease in the performance of the polymer.

[0007] The present invention has been made in view of the above-mentioned conventional problems, and has as its object to provide a stable reaction product containing a vinyl monomer having a higher concentration of a metal salt without using a solubilizing agent. Is to provide. Further, another object of the present invention is to obtain a polymerizable composition containing the above reaction product by (co) polymerization, and to obtain chemical resistance such as alkali resistance and water resistance, tensile strength and tear strength. To provide a polymer with excellent physical properties such as mechanical strength, toughness, heat resistance, oil resistance, weather resistance, and transparency, and low creep such as compression set and tensile elongation (low creep). is there.

[0008]

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 high concentration of a metal salt. As a result, a metal salt is reacted with a mixture of two or more unsaturated acids selected from the group of specific unsaturated acids such as a monomer obtained by acrylate-modifying ethylene glycol monophthalate and a metal compound, thereby forming a metal salt. It has been found that a reaction product containing a vinyl monomer can be produced in a simple process with good productivity and at low cost, and the present invention has been completed.

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 comprise a mono-phthalic acid whose aromatic ring may be hydrogenated. Including a vinyl monomer having a metal salt obtained by reacting a mixture of two or more unsaturated acids selected from the group of unsaturated acids which are (alkylene glycol (meth) acrylate) esters with a metal compound in a solvent. It is characterized by.

In order to solve the above-mentioned problems, the reaction product according to the present invention comprises a mixture of the above two or more unsaturated acids represented by the general formula (1) or the general formula (2).

[0011]

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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 solvent is a vinyl monomer 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 structure, the aromatic ring may have a substituent, and the phthalic acid mono (alkylene glycol (meth) may be hydrogenated.
Acrylate) by using a mixture of two or more unsaturated acids selected from the group of unsaturated acids that are esters,
The solubility of the vinyl monomer having a metal salt obtained by reacting the mixture of the unsaturated acid with the metal compound in the reaction system (unsaturated acid, solvent and reaction product) is improved. Therefore, even without using a solubilizing agent, the concentration of the vinyl monomer having a metal salt in the reaction product finally formed can be made higher than before. In addition, a liquid and transparent reaction product containing a vinyl monomer having a metal salt into which a metal salt is reliably introduced can be produced.

Thus, a stable reaction product containing a vinyl monomer having a higher concentration of a metal salt can be provided without using a solubilizing agent substantially. Also,
The polymer obtained by (co) polymerizing the polymerizable composition containing the above reaction product contains substantially no solubilizing agent. Therefore, a polymer having excellent chemical resistance such as alkali resistance and water resistance can be produced. In the present invention, "substantially no use of a solubilizing agent" means that
1.0% by weight or less, more preferably 0.5% by weight or less, further preferably 0.1% by weight
Hereinafter, it is most preferably referred to as 0% by weight. In the present invention, the "polymerizable composition" refers to a reaction product itself obtained by reacting a mixture of an unsaturated acid and a metal compound in a solvent, or the reaction product and a vinyl monomer or the like. A mixture with a (co) polymerizable substance.

The above reaction product contains a vinyl monomer having a metal salt in a higher concentration than before.
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, a polymer excellent in various physical properties such as mechanical strength such as tensile strength and tear strength, toughness, heat resistance, oil resistance, weather resistance, and transparency can be produced. 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 po
It can be manufactured in t (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.

[0019]

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)

[0020]

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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. The compound is produced by reacting a mixture of two or more unsaturated acids selected from the group of unsaturated acids represented by the following formulas with a metal compound in 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. The general formula (3)
Or general formula (4)

[0023]

Embedded image

(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 is, 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 are used in combination of two or more.

[0027]

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The unsaturated acid used in the present invention is at least two kinds of unsaturated acids represented by the general formula (1), the general formula (2), the general formula (3) or the general formula (4). Used as a mixture of unsaturated acids. When only one of the above-mentioned unsaturated acids is used, a reaction product of an unsaturated acid and a metal compound described later is separated or solidified. Therefore, it is difficult to obtain a stable liquid reaction product containing a vinyl monomer having a high concentration of a metal salt, which is the object of the present invention. Since the reaction product according to the present invention is in a liquid state, it is easy to handle and can be widely used for various purposes.

The proportion of one kind of unsaturated acid in the mixture of two or more kinds of unsaturated acids is preferably in the range of 10 to 90 mol%, more preferably in the range of 20 to 80 mol%.
By setting the proportion of one kind of unsaturated acid in the mixture of two or more kinds of unsaturated acids to be within the above range, a vinyl monomer having a metal salt obtained by reacting the mixture of unsaturated acids with a metal compound can be used. The solubility in the reaction system is further improved. Therefore, it becomes easier to obtain a reaction product containing a vinyl monomer having a high concentration of a metal salt without using a solubilizing agent.

The mixture of two or more unsaturated acids is a vinyl monomer having a carboxyl group (hereinafter referred to as vinyl monomer A).
May be further included. However, when the above mixture further contains vinyl monomer A, the amount of 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 not preferable because it becomes difficult to obtain a uniform liquid reaction product aimed at by the present invention. In the present invention, the vinyl monomer A has the general formula (1) and the general formula (2)
Is not included.

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. And organometallic compounds such as metal alcoholates such as metal propylate and metal butyrate, but are not particularly limited thereto. 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.

A reaction product containing a vinyl monomer having a metal salt according to the present invention is obtained by reacting the above-mentioned mixture of unsaturated acids with a metal compound in a solvent. The above-mentioned solvent is used for facilitating the reaction or adjusting the viscosity of the finally obtained reaction product to a range that can be easily handled. The amount of the solvent used is not particularly limited, but in order to facilitate the reaction, the amount of the vinyl monomer having a metal salt contained in the reaction product is more preferably 30 to 90% by weight. Within the range, more preferably 50 to
In the range of 90% by weight, most preferably 70-90% by weight
Is set to be within the range. Further, when the reaction product according to the present invention is used in the next step by blending it with a plastic substance such as rubber or a substance such as a filler compound,
The reaction may be performed in advance in the presence of these substances.

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 needed 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, and 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 type of the solvent in the present invention is not particularly limited.
When a mixture with vinyl monomer B) is used as the polymerizable composition, vinyl monomer B may be used as a solvent. As the vinyl monomer B, any of a monofunctional vinyl monomer and a polyfunctional vinyl monomer can be used. Examples of the monofunctional vinyl monomer include aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, acryl Acrylates such as methoxyethyl acrylate; methyl methacrylate, butyl methacrylate,
Methacrylic esters such as ethoxyethyl methacrylate and diethylene glycol methacrylate monomethyl ether; vinyl monomers containing a nitrile group such as acrylonitrile and methacrylonitrile; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; n-butyl vinyl ether; alkyl vinyl ethers such as sec-butyl vinyl ether; and the like, but are not particularly limited. Examples of the polyfunctional vinyl monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, di (meth) acrylate of ethylene glycol diphthalate; and divinyl benzene, chloroprene, isoprene, butadiene and the like. Functional vinyl monomers; trifunctional vinyl monomers such as trimethylolpropane tri (meth) acrylate; and the like, but are not particularly limited thereto.
One of the above solvents may be used alone, or two or more thereof may be used in combination. In the present invention, the vinyl monomer B does not include a vinyl monomer having an unsaturated acid and a metal salt represented by the general formulas (1) and (2).

As described above, the reaction product produced using the vinyl monomer B as a solvent is a polymerizable composition containing the vinyl monomer B, which can be polymerized as it is. . Therefore, by using the vinyl monomer B as a solvent, the reaction product can be obtained in a preferable form as a raw material used in a polymerization step after production. Therefore, the solvent in the present invention is not particularly limited, but it is preferable to use the vinyl monomer B. If necessary, an organic solvent such as toluene can be used in a compounding amount within a range that does not hinder the subsequent polymerization step.

The equivalent ratio (unsaturated acid / metal compound) in the reaction between the unsaturated acid and the metal compound depends on the composition of the unsaturated acid, the type of the metal compound, the combination of the two, the use of the reaction product, the reaction product What is necessary is just to set according to various physical properties etc. which are requested | required of a thing, and although it does not specifically limit, 1.0
It is more preferably in the range of -1.2.

The method of reacting an unsaturated acid with a metal compound in a solvent is not particularly limited. Specifically, for example, a mixture of an unsaturated acid and a metal compound are mixed in a solvent. Thereafter, a method of stirring at room temperature or under heating may be mentioned. As a result, the reaction proceeds, a vinyl monomer having a metal salt is formed, and a reaction product in which the vinyl monomer having the metal salt is dissolved in a solvent is obtained. The method for mixing the mixture of the unsaturated acid and the metal compound is not particularly limited.For example, a solvent is added to an unsaturated acid to dissolve it to form an unsaturated acid solution, and the metal compound is added to the unsaturated acid solution. A method of mixing a metal compound in a solvent and then mixing a mixture of unsaturated acids; a method of simultaneously mixing a mixture of unsaturated acids and a metal compound in a solvent; and the like. Of the above exemplified methods, the method is more preferable.

Whether the reaction between the mixture of unsaturated acids and the metal compound has been completed is determined, for example, when the metal compound used is insoluble in the reaction system, the reaction system is uniform and transparent at room temperature or is milky ( (Colloidal dispersion). The point at which a reaction product that is uniform and transparent or milky at room temperature is obtained is the end point of the reaction. Therefore, the operation such as stirring may be ended at the above time. The reaction conditions such as the reaction temperature and the reaction time may be any conditions under which the above-mentioned reaction proceeds and the substances of the reaction system (unsaturated acid, solvent, metal compound and reaction product) are not altered.
There is no particular limitation.

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

Since the liquid reaction product according to the present invention uses a mixture of unsaturated acids having a specific skeleton as a raw material, the vinyl monomer having a metal salt can be used as a solvent without using a solubilizing agent. Obtained in a state of being dissolved in
The concentration of the vinyl monomer having a metal salt in the reaction product can be made relatively high. Then, the polymer obtained by (co) polymerizing the polymerizable composition containing the above 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.

Since the reaction product according to the present invention contains a vinyl monomer having a stable and high-concentration metal salt, it 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 a high concentration into the obtained polymer skeleton. Therefore, the degree of ionic crosslinking of the polymer can be sufficiently increased. Therefore, it is excellent in various physical properties such as mechanical strength such as tensile strength and tear strength, toughness, heat resistance, oil resistance, weather resistance, and transparency, and has small creep such as compression set and tensile elongation ( (Low creep) polymers can be produced.

The method of (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, reaction temperature, and reaction time in the above-mentioned 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.

The polymer obtained by (co) polymerizing the polymerizable composition according to the present invention can be applied to a wide range of uses. For example, by forming a polymerizable composition comprising a reaction product and an alkyl acrylate such as ethyl acrylate into a continuous sheet, 1 pot is obtained.
A tough metal crosslinked acrylic elastomer can be produced in the process. The above-mentioned metal crosslinked acrylic elastomer does not contain a solubilizing agent, and thus has high waterproofness. Further, by casting polymerization of the above polymerizable composition, damping rubber,
It can be used for applications such as foams. In addition, by performing bulk polymerization of a polymerizable composition comprising a reaction product and an alkyl methacrylate such as methyl methacrylate, a thermoplastic resin having improved heat resistance, radiation shielding effect, and the like can be produced. Further, the reaction product and n-
By polymerizing a polymerizable composition comprising an alkyl acrylate such as butyl acrylate with heat or radiation, it is possible to produce a pressure-sensitive adhesive having excellent heat resistance, cohesive strength, adhesive strength, and excellent adhesive properties such as tackiness. . The above adhesive is
Can be widely used for adhesive tapes, labels, sheets, etc. In addition, the polymerizable composition comprising the above reaction product and an alkyl acrylate can be bulk-polymerized to be similarly used as a hot-melt adhesive having excellent physical properties. Emulsions obtained by emulsion polymerization of a polymerizable composition comprising a reaction product and styrene, (meth) acrylate, and the like can be used as functional paints such as antifouling paints, vibration damping paints, and UV curable paints. Further, by vulcanizing a polymerizable composition comprising a reaction product and an unvulcanized rubber with a peroxide or the like, a vulcanized rubber excellent in hardness, strength, toughness and the like can be produced. The above crosslinked rubber can be widely used for tires, high-strength rubbers, golf balls, heat-resistant rubbers, and the like. Other uses of the polymer obtained by (co) polymerizing the polymerizable composition include, for example, adhesives, sealants, thermosetting resin compounds,
And asphalt modifiers.

[0049]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. In the Examples and Comparative Examples, “parts” indicates “parts by weight”. Further, various physical properties of the polymer (crosslinked rubber), that is, type A durometer hardness, tensile strength (tensile breaking strength), tensile elongation (tensile breaking elongation), and compression set are determined according to JIS K6301.
And the like.

The tensile strength at break and tensile elongation at break were measured using a dumbbell No. 2 type test piece having a thickness of 3 mm at a tensile speed of 500 mm / min. The measurement of the compression set was performed using a cylindrical test piece having a diameter of 20 mm and a thickness of 12 mm.
After compressing at a compression ratio of 25% at 90 ° C. for 70 hours, the load was removed and the film was gradually cooled, and the thickness was measured 30 minutes after the load was removed.

The alkali resistance was determined by immersing a test piece in a 5% aqueous sodium hydroxide solution and measuring the rate of change in weight after standing at 25 ° C. for a certain period.

The amount of vinyl monomer having a metal salt in the reaction product was determined by accurately weighing about 1 g of a sample in an aluminum dish having a diameter of 5 cm, diluting with acetone, air-drying, and drying in an oven.
The nonvolatile content after heating at 00 ° C. for 30 minutes was weighed and determined.

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 monomer solution of a vinyl monomer having a metal salt was synthesized. In a 1 L reactor equipped with a stirrer, cooling tube, thermometer and gas inlet tube, the above unsaturated acid (1) 155.
5 parts and another unsaturated acid mono (ethylene glycol) phthalate methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .;
148.2 parts (trade name: “NK Ester CB-1”) (the molar ratio of unsaturated acid (1) to mono (ethylene glycol) phthalate methacrylate is 1: 1), and n-butyl acrylate as a solvent 82.2 parts and dissolved. Further, 40.1 parts of zinc oxide (two kinds of zinc flowers manufactured by Sakai Chemical Co., Ltd.) as a metal compound was 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 4 hours in a mixed gas stream, and then diluted with 24.0 parts of n-butyl acrylate as a solvent. 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) was 0.9 Pa · s (25 ° C.). Further, the reaction product (1) 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 zinc salt of the two unsaturated acids. The amount of the vinyl monomer having a metal salt in the reaction product (1) was 318 parts (70.5% by weight, theoretical value 7
2.1% 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.

Next, a polymerizable composition was prepared using the above reaction product (1), and polymerized to obtain a polymer.
That is, 13.2 parts of the above reaction product (1), 66.3 parts of n-butyl acrylate, and 30 parts of methyl methacrylate
And 2.5 parts of dimethacrylate of diethylene glycol diphthalate were mixed to form a polymerizable composition, into which 0.5 part of a 55% solution of methyl ethyl ketone peroxide in dimethyl phthalate as a radical polymerization initiator, and a polymerization accelerator And 0.5 parts of a mineral spirit solution of cobalt octenoate (cobalt content: 8% by weight). Then, the obtained mixture was injected into a cell assembled with a silicone spacer and a glass plate, and 6
After polymerization at 5 ° C. for 7 hours, polymerization was further performed at 120 ° C. for 2 hours. Table 2 shows the performance of the obtained polymer (hereinafter, referred to as crosslinked rubber (1)).

Example 2 In the synthesis of a monomer solution of a vinyl monomer having a metal salt in Example 1, 155.5 parts of unsaturated acid (1) was added to 63.2 parts, and mono (ethylene glycol) phthalate methacrylate 148 was used. .2 parts 2
Except for changing to 40.5 parts (the molar ratio of unsaturated acid (1) to mono (ethylene glycol) phthalate methacrylate is 1: 4), the same reaction and operation as in Example 1 were carried out,
A reaction product containing a vinyl monomer having a metal salt according to the present invention (hereinafter, referred to as reaction product (2)) was obtained. 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 1.2 Pa · s (25
° C). Further, the reaction product (2)
Even after standing for months, it was uniform and transparent, 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. The amount of vinyl monomer having a metal salt in the reaction product (2) was 320 parts (71.0% by weight, theoretical value: 72.1% by weight). Table 1 shows the results.

Next, a polymer (hereinafter referred to as a crosslinked rubber (2)) was obtained in exactly the same manner as in Example 1 except that the above reaction product (2) was used. Table 2 shows the performance of the obtained crosslinked rubber (2).

Example 3 In the synthesis of the monomer solution of the vinyl monomer having the metal salt of Example 1, 155.5 parts of the unsaturated acid (1) was replaced with mono (propylene glycol) phthalate acrylate (Shin-Nakamura Chemical Co., Ltd.) 151.8 parts of mono (ethylene glycol) phthalate methacrylate 14
The same reaction and operation as in Example 1 were carried out except that 8.2 parts was changed to 151.8 parts (the molar ratio of mono (propylene glycol) phthalate acrylate to mono (ethylene glycol) phthalate methacrylate was 1: 1). Do
A reaction product containing a vinyl monomer having a metal salt according to the present invention (hereinafter, referred to as reaction product (3)) was obtained. 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) was 0.3 Pa · s (25 ° 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 zinc salt of the two unsaturated acids. The amount of vinyl monomer having a metal salt in the reaction product (3) was 319 parts (70.7% by weight, theoretical value 72.0% by weight). Table 1 shows the results.

Next, a polymer (hereinafter referred to as a crosslinked rubber (3)) was obtained in exactly the same manner as in Example 1 except that the above reaction product (3) was used. Table 2 shows the performance of the obtained crosslinked rubber (3).

Example 4 In the synthesis of a monomer solution of a vinyl monomer having a metal salt in Example 1, diethylene glycol methacrylate monomethyl ether (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of n-butyl acrylate as a solvent; Example 1 except that the trade name “NK ester M-20G”) was used and the reaction time was changed from 4 hours to 8 hours.
By performing the same reaction and operation as described above, a reaction product containing a vinyl monomer having a metal salt according to the present invention (hereinafter, referred to as reaction product (4)) was obtained. The obtained reaction product (4)
It was uniform and almost transparent milky white, and maintained the same uniform and almost transparent state even after cooling to room temperature. The viscosity of the reaction product (4) is 3.0 Pa · s (25
° C). Further, the reaction product (4)
Even after standing for months, it was uniform and almost transparent, and maintained its initial state. From this, it was confirmed that the total amount of the added zinc oxide was converted into zinc salts of two unsaturated acids. The amount of the vinyl monomer having a metal salt in the reaction product (4) was 319 parts (70.7% by weight, theoretical value 72.0% by weight). Table 1 shows the results.

Example 5 In the synthesis of a monomer solution of a vinyl monomer having a metal salt of Example 1, diethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; trade name) was used instead of n-butyl acrylate as a solvent. Reaction product containing a vinyl monomer having a metal salt according to the present invention by performing the same reaction and operation as in Example 1 except that “NK ester 2G”) is used and the reaction time is changed from 4 hours to 8 hours. (Hereinafter, referred to as reaction product (5)).
The obtained reaction product (5) was in a uniform and almost transparent milky white state, and kept the same uniform and almost transparent state even after cooling to room temperature. Reaction product (5)
Was 4.1 Pa · s (25 ° C.). further,
The reaction product (5) was uniform and almost transparent even after standing 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 into zinc salts of two unsaturated acids. The amount of the vinyl monomer having a metal salt in the reaction product (5) was 325 parts (72.0% by weight, theoretical value of 72.1%).
Wt%). Table 1 shows the results.

Example 6 A polymerizable composition was prepared using the reaction product (1) obtained in Example 1, and polymerized to obtain a polymer. That is, the above reaction product (1) 3.
13 parts and 96.87 parts of n-butyl acrylate were 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 poured into a cell composed of a 0.5 mm thick silicone spacer and a glass plate / release paper, polymerized at 80 ° C. for 90 minutes, and further polymerized at 160 ° C. for 30 minutes. Obtained polymer (adhesive sheet)
Was a pressure-sensitive adhesive sheet having a ball tack (J-DOW method) of 30 and excellent adhesiveness and excellent tear strength.

COMPARATIVE EXAMPLE 1 In the synthesis of the monomer solution of the vinyl monomer having a metal salt of Example 1, no unsaturated acid (1) was used at all, and 148.2 parts of mono (ethylene glycol) phthalate methacrylate were added to 296 parts. The same reaction and operation as in Example 1 were performed, except that the molar ratio of unsaturated acid (1) and mono (ethylene glycol) phthalate methacrylate was changed to 0: 1. The molar ratio of zinc oxide to mono (ethylene glycol) phthalate methacrylate was 1.0: 2.1. The appearance of the resulting liquid product was uneven and cloudy. Then, when the product was cooled to room temperature, it became a white solid state, and the uniform and liquid reaction product aimed at by the present invention could not be obtained. Table 1 shows the results.

Comparative Example 2 In the synthesis of the monomer solution of a vinyl monomer having a metal salt of Example 1, no mono (ethylene glycol) phthalate methacrylate was used at all, and 155.5 parts of the unsaturated acid (1) was used in 311 parts. The same reaction and operation as in Example 1 were carried out except that the molar ratio of the unsaturated acid (1) to mono (ethylene glycol) phthalate methacrylate was changed to 1: 0. The molar ratio of zinc oxide to unsaturated acid (1) was 1.0: 2.1. The appearance of the resulting liquid product was uneven and cloudy. Then, when the product was cooled to room temperature, it turned into a white solid state, and the uniform and liquid reaction product aimed at by the present invention could not be obtained. Table 1 shows the results.

Comparative Example 3 A 500-mL reactor equipped with a stirrer, a cooling pipe, a thermometer, and a gas introduction pipe was charged with n-
208 parts of butyl acrylate and 31 parts of zinc oxide were charged. On the other hand, 28 parts of acrylic acid and 34 parts of methacrylic acid (the molar ratio of acrylic acid to methacrylic acid is 1:
1) was mixed to prepare a mixed solution. Next, while stirring the content in the reactor under a mixed gas stream, the above-mentioned mixed solution was dropped into the content in the reactor over 30 minutes. The molar ratio between zinc oxide and two unsaturated acids (acrylic acid and methacrylic acid) was 1.0: 2.1. During this time, in order to suppress heat generation due to the neutralization reaction occurring in the reactor, the amount of the mixed solution dropped was adjusted so that the temperature of the contents did not exceed 70 ° C. After the completion of the dropping of the mixture, the reaction was continued while maintaining the temperature of the contents in the reactor at 70 ° C. There was no change in appearance, and it was cloudy. When the product was cooled to room temperature, precipitation occurred, and the uniform and liquid reaction product aimed at by the present invention could not be obtained. Table 1 shows the results.

Comparative Example 4 In Comparative Example 3, in addition to acrylic acid and methacrylic acid, 7.9 parts of water as a solubilizing agent (zinc oxide and two kinds of unsaturated acids (acrylic acid) And methacrylic acid) and water at a molar ratio of 1: 2.1:
1.2) Except for using the same operation as in Comparative Example 3,
By performing the reaction, a reaction product (hereinafter, referred to as a comparative reaction product) was obtained. The appearance of the obtained comparative reaction product is
One hour after the completion of the dropping of the mixture, the mixture was uniform and transparent, and even after cooling to room temperature, the uniform and transparent state was maintained. The viscosity of the comparative reaction product is 2.0 ×
It was 10 ⁻³ Pa · s (25 ° C.). The amount of vinyl monomer having a metal salt in the comparative reaction product was 78.
8 parts (25.5% by weight, theoretical value 28.6% by weight). Further, the comparative reaction product 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 zinc salts of the two unsaturated acids (acrylic acid and methacrylic acid). Table 1 shows the results.

Next, a polymer was synthesized using the above comparative reaction product. That is, exactly the same reaction and operation as in the method of Example 1 were carried out except that 13.2 parts of the reaction product (1) in Example 1 was used in place of 11.6 parts of the above-mentioned comparative reaction product. And a polymer (hereinafter, referred to as a comparative crosslinked rubber). Table 2 shows the performance of the comparative crosslinked rubber.
Shown in

[0070]

[Table 1]

Table 1 above summarizes the synthesis examples and comparative examples of the reaction product containing the vinyl monomer having a metal salt according to the present invention. Examples 1 to 5 shown in Table 1
As is clear from the results, it was found that the reaction product according to the present invention can be easily obtained as a liquid reaction product having a good appearance without using a solubilizing agent.
On the other hand, from the results of Comparative Examples 1 and 2, it was found that even when one kind of unsaturated acid was reacted with a metal compound in a solvent, a reaction product having good appearance could not be obtained. Also,
From the results of Comparative Examples 3 and 4, when acrylic acid and methacrylic acid were used in combination as two types of unsaturated acids, a reaction product having a good appearance was obtained unless water was used as a solubilizing agent. I found that I could not get. When acrylic acid and methacrylic acid are used in combination as two types of unsaturated acids, a reaction product having a good appearance can be obtained by using water as a solubilizing agent. It was found that the content of the vinyl monomer having a metal salt in the reaction product was lower than that of the reaction products obtained in Examples 1 to 5.

[0072]

[Table 2]

Table 2 above summarizes the performance of the crosslinked rubber which is the polymer according to the present invention, together with the performance of the comparative crosslinked rubber of the comparative example. The crosslinked rubber is a polymer obtained by (co) polymerizing a polymerizable composition prepared using a reaction product containing a vinyl monomer having a metal salt obtained in the present invention. On the other hand, the comparative crosslinked rubber of the comparative example is prepared using a comparative reaction product obtained by using a mixture of acrylic acid and methacrylic acid and a solubilizing agent.

From the results of Examples 1 to 3 shown in Table 2, the crosslinked rubbers (1) to
(3) is excellent in balance between strength / elongation characteristics and low creep property (low compression set), which are basic properties of crosslinked rubber, and alkali resistance which is a weak point of metal crosslinking. Proved to be excellent. On the other hand, Comparative Example 4
The comparative crosslinked rubber was excellent in the above basic performance, but showed a large change in weight in the alkali resistance test. That is, the comparative crosslinked rubber is a crosslinked rubber (1) to
Compared with (3), it was found that the basic performance as a crosslinked rubber was equally excellent, but the alkali resistance was significantly inferior.

As described above, a liquid reaction product containing a vinyl monomer having a high concentration of a metal salt and having a good appearance according to the present invention can be easily obtained. The reaction product according to the present invention, the raw material used is inexpensive,
Moreover, the manufacturing process is simple. 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, a polymer containing a metal salt having excellent performance such as alkali resistance can be obtained.
You can easily get at the pot.

[0076]

As described above, the reaction product of the present invention is:
The aromatic ring may have a substituent, and further, two or more kinds selected from the group of unsaturated acids which are mono (alkylene glycol (meth) acrylate) esters of phthalic acid in which the aromatic ring may be hydrogenated A mixture of unsaturated acids;
This is a configuration including a vinyl monomer having a metal salt obtained by reacting with a metal compound in a solvent. The reaction product of the present invention comprises:
As described above, the mixture of the two or more unsaturated acids has a configuration 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 constitution in which the solvent is a vinyl monomer.

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.

Thus, without using a solubilizing agent,
This has the effect of providing a stable liquid reaction product containing a vinyl monomer having a high concentration of a metal salt. In addition, various physical properties such as chemical resistance such as alkali resistance and water resistance, mechanical strength such as tensile strength and tear strength, toughness, heat resistance, oil resistance, weather resistance, transparency, etc., which do not contain a solubilizer. And a polymer containing a metal salt having low creep such as compression set and tensile elongation (low creep) can be provided.

[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.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J027 AC02 AC03 AC04 AC06 BA04 BA05 BA07 BA17 BA18 BA19 CB03 CC02 4J100 AL08P AL16P BA08P BA15P BA16P BA17P BB01P BB03P BC04P BC43P CA03 CA04 FA03

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 a mixture of two or more kinds of unsaturated acids described above with a metal compound in a solvent. 2. A mixture of the above two or more unsaturated acids is represented by 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 solvent is a vinyl monomer. 4. A polymer obtained by (co) polymerizing a polymerizable composition containing the reaction product according to claim 1, 2 or 3.