JP2006219506A - Radically polymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radically polymerizable composition that reduces the amount of formaldehyde, formed by a side-reaction and diffused in the course of a radical polymerization reaction, without hindering cure by the radical polymerization reaction, and to provide a manufacturing method of a radical polymerization-cured product that gives a reduced amount of formaldehyde diffused when the composition is subjected to radical polymerization without hindering cure by the radical polymerization reaction of the composition. <P>SOLUTION: The radically polymerizable composition comprises a radically polymerizable compound, a radical polymerization initiator and catechin. The manufacturing method of the radical polymerization-cured product that gives a reduced amount of formaldehyde diffused when the composition is subjected to radical polymerization comprises radically polymerizing the composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a radically polymerizable composition with reduced formaldehyde emission. Moreover, it is related with the manufacturing method of the radical polymerization hardened | cured material with which the quantity of formaldehyde diffused when carrying out radical polymerization of a composition was reduced.

In recent years, VOC (Volatile Organic Compound), which is considered to have a possibility of adversely affecting the human body from building materials and furniture, has become a problem of polluting indoor air. Representative examples of VOC include formaldehyde, toluene, xylene and the like. In particular, formaldehyde is contained in plywood and furniture adhesives that have been used for flooring materials in the past, and various improvements such as removal of causative substances and reduction of indoor concentration by physical adsorption are being promoted. It has been. For example, a composition in which a component that absorbs formaldehyde or the like is added to a synthetic resin is known (see Patent Documents 1 to 3).
On the other hand, formaldehyde may be generated during the curing reaction of the radical polymerizable composition. For example, an unsaturated polyester resin using styrene, a metacle flooring material using vinyl ester or methacrylic acid ester, etc. is a material that is mixed with a peroxide as a radical polymerization initiator at the construction site, and is radically polymerized and cured. In some cases, formaldehyde may be released by side reactions during radical polymerization reactions. When the radical polymerizable composition is used in combination with a known formaldehyde absorbent, there is a problem that the radical polymerizable property may be inhibited or the formaldehyde absorption effect may not be sufficiently exhibited.
Examples of compounds that absorb formaldehyde include urea, thiourea and their derivatives, sulfites such as sodium sulfite and potassium pyrosulfite, amines such as methanolamine and ethanolamine, ammonium salts such as ammonium sulfate and ammonium phosphate, Formaldehyde is known as a porous material such as phenols such as resorcinol and pyrogallol, compounds containing acetoacetoxy groups such as acetoacetoxymethyl methacrylate, activated carbon, zeolite, and diatomaceous earth. These aldehyde absorbing materials are blended in a paint and have the purpose of adsorbing formaldehyde in the air, and do not efficiently absorb aldehyde generated during curing of the radical polymerizable composition (Patent Documents 1 to 3). reference.).
That is, there is no known radically polymerizable composition that reduces the amount of formaldehyde that is generated and dissipated by a side reaction during the radical polymerization reaction without inhibiting the curing by the radical polymerization reaction.

JP-A-11-226100 JP 2000-37447 A JP 2001-149456 A

An object of the present invention is to provide a radically polymerizable composition in which the amount of formaldehyde generated and diffused by a side reaction during a radical polymerization reaction is reduced without inhibiting curing due to the radical polymerization reaction. It is another object of the present invention to provide a method for producing a radical polymerization cured product in which the amount of formaldehyde released when radically polymerizing the composition is reduced without inhibiting the composition from being cured by radical polymerization reaction.

In order to solve the above problems, the radically polymerizable composition of the invention described in claim 1 is characterized by containing a radically polymerizable compound, a radical polymerization initiator, and catechin.
The radically polymerizable composition of the invention according to claim 2 is obtained by polymerizing a vinyl monomer at a temperature of 170 ° C. to 350 ° C. as a radical polymerizable compound in the invention of claim 1. It comprises a polymer C having a methacryloyl group obtained by reacting a functional group A with a functional group B using a polymer A having A and a compound B having a methacryloyl group and a functional group B as raw materials.
The radically polymerizable composition of the invention described in claim 3 is characterized in that in the invention described in claim 1 or 2, dicyclopentenyloxyethyl methacrylate is contained as the radically polymerizable compound.
According to a fourth aspect of the present invention, there is provided a method for producing a radical polymerization cured product, wherein the radical polymerizable composition according to any one of the first to third aspects is radically polymerized.

A radical polymerizable composition was obtained in which the amount of formaldehyde generated and dissipated by the side reaction during the radical polymerization reaction is reduced without inhibiting the curing by the radical polymerization reaction. Moreover, the manufacturing method of the radical polymerization hardened | cured material with which the quantity of formaldehyde diffused when carrying out radical polymerization of a composition was reduced, without inhibiting the hardening by the radical polymerization reaction of a composition was provided.

  In this specification, (meth) acryl means acryl or methacryl, and (meth) acrylate means acrylate or methacrylate. The number average molecular weight and the weight average molecular weight are values obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC) into polystyrene using tetrahydrofuran as a solvent.

  The radically polymerizable compound is a component that imparts radical polymerizability to the composition. The radical polymerizable compound may be a radical polymerizable monomer or a polymer having a radical polymerizable group.

  The polymer having a radical polymerizable group is produced by a known method. For example, it can be obtained by a reaction between a polymer having an epoxy group and (meth) acrylic acid or a reaction between a polymer having a carboxyl group and glycidyl (meth) acrylate. Unsaturated polyesters can also be used. A composition containing a polymer having a radical polymerizable group as the radical polymerizable compound is preferred because it tends to be excellent in curability and cured product properties.

  Among the polymers having a radical polymerizable group, as a radical polymerizable compound, a polymer A having a functional group A obtained by polymerizing a vinyl monomer at a temperature of 170 ° C. to 350 ° C., a methacryloyl group, and a functional group B A polymer C having a methacryloyl group obtained by reacting a functional group A and a functional group B using a compound B having a silane as a raw material is particularly preferable. Examples of combinations of functional groups A and B include a combination of an epoxy group and a carboxyl group, and a combination of a carboxyl group and an epoxy group. The number average molecular weight of the polymer C is preferably 500 to 10,000, more preferably 1000 to 7000.

  The radically polymerizable monomer is a useful component for controlling the viscosity of the composition or controlling the curability of the composition, such as imparting fluidity to the radically polymerizable composition. Examples of radical polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Examples include (meth) acrylic acid esters such as dicyclopentenyloxypropyl (meth) acrylate, styrene, α-methylstyrene, acrylonitrile, vinyl acetate, and the like. Dicyclopentenyloxyethyl (meth) acrylate and dicyclopentenyloxypropyl (meth) acrylate are preferred because the resulting radically polymerizable composition has no odor or is weak.

  The ratio of the polymer having a radical polymerizable group and the radical polymerizable monomer is not particularly limited, but the ratio of the polymer having a radical polymerizable group is 1 to 99 masses based on 100 parts by mass of the radical polymerizable compound. Is preferably 5 to 95 parts by mass, more preferably 10 to 90 parts by mass, and most preferably 20 to 80 parts by mass.

  Known radical polymerization initiators can be used. It is preferable that the usage-amount of a radical polymerization initiator is 0.2-20 mass parts on the basis of 100 mass parts of total amounts of a radically polymerizable compound. The amount of radical polymerization initiator shown here is the net amount excluding inert substances such as solvents, excipients, and supporting components, and the radical polymerization initiator is composed of a plurality of components such as redox initiators. Means the total amount of them.

The radical polymerization initiator is particularly preferably a redox initiator composed of an oxidizing agent and a reducing agent.
The oxidizing agent that is a constituent component of the redox initiator is not particularly limited, but is preferably an organic peroxide. Examples of the organic peroxide include diacyl peroxide, peroxyester, hydroperoxide, dialkyl peroxide, ketone peroxide, peroxyketal, alkyl perester, and parker cart. . Of these, diacyl peroxide type or ketone peroxide type are preferable. These are preferably used in a diacyl peroxide type in an amount of 0.1 to 10 parts by mass, and used in a ketone peroxide type in an amount of 0.5 to 20 parts by mass.
These organic peroxides are appropriately selected and used according to various conditions during construction such as the composition kneading conditions and the film curing temperature obtained by applying the composition. Since these organic peroxides are excellent in safety, they are preferably dissolved or dispersed in an inert liquid or supported on a powder to have a concentration of 70% by mass or less, and preferably 20 to 60% by mass. Is more preferable. A paste-like or powder-like one having an organic peroxide content of 20 to 60% by mass is particularly preferred.

Various reducing agents can be used, and examples thereof include tertiary amines, quaternary ammonium salts, and metal soaps having metals such as cobalt, vanadium, and manganese.
The tertiary amine is preferably one in which at least one aromatic residue is directly bonded to the nitrogen atom. Examples thereof include N, N-dimethylaniline and N, N-dimethyl-p-toluidine. Particularly preferred are tertiary amines having one or more hydroxyl groups, such as N, N-di (β-hydroxyethyl) -aniline, N-methyl N-hydroxyethylaniline, N-ethyl N-β- Hydroxyethyl-aniline, N, N-di (β-hydroxyethyl) -m-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine, N-methyl N-βhydroxyethyl-m-toluidine, N-ethyl N-β-hydroxyethyl-m-toluidine, N, N-di (β-hydroxyethyl) m-chloroaniline and the like can be mentioned.

  When a redox initiator is used, the oxidizing agent and the reducing agent are preferably stored so as not to come into contact until immediately before use of the radically polymerizable composition. For example, a method of mixing a main agent containing a radical polymerizable compound and a reducing agent and an auxiliary agent containing an oxidizing agent immediately before use can be employed.

  Catechin is a component for absorbing formaldehyde generated in the radical polymerization reaction of the composition and reducing formaldehyde emission without inhibiting the radical polymerizability of the composition, particularly the surface curability. Examples of catechins include tea catechins such as polyphenols extracted from green tea and the like, and active ingredients that react with formaldehyde include epicatechin gallate and epigallocatechin gallate. In addition to green tea, from black tea, oolong tea, puer tea, leaves, stems, xylem, bark, roots, fruits, seeds, and mixtures thereof, water, hot water, organic solvents, hydrous organic solvents and mixtures thereof Is extracted from

  The radically polymerizable composition of the present invention may be added with a polymer that does not have radically polymerizable properties. By adding a polymer having no radical polymerizability, the curability of the composition and the physical properties of the cured product can be controlled. Examples of the polymer having no radical polymerizability include vinyl polymers such as (meth) acrylic polymers and other thermoplastic resins.

  The radically polymerizable composition of the present invention may be added with wax. When a wax is added, it is preferable because the curability of the composition surface is excellent. Examples of the wax include paraffin wax having a melting point of 40 ° C. or higher, higher fatty acids such as polyethylene wax and stearic acid. When the melting point is less than 40 ° C., the effect of improving the curability may not be sufficiently exhibited. The addition amount of the wax is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass based on 100 parts by mass of the radical polymerizable compound. If the addition ratio of the wax is too small, a sufficient effect of improving the curability may not be obtained.

  The radically polymerizable composition of the present invention may be added with a polyvalent metal salt or a polyvalent metal complex, and in this case also, the curability is improved. As the polyvalent metal salt, a metal salt of a higher fatty acid is generally preferable, for example, a polyvalent metal salt such as naphthenic acid or octenoic acid, and the polyvalent metal includes calcium, copper, zirconium, manganese, cobalt, lead, iron. And vanadium. Of these, cobalt naphthenate, lead naphthenate, cobalt octenoate, and lead octenoate are preferred. As the polyvalent metal complex, a complex of acetylacetone is well known, and examples thereof include cobalt acetyl acetate and manganese acetyl acetate. These addition amounts are preferably 0.05 to 5 parts by mass based on 100 parts by mass of the radical polymerizable compound.

  The radically polymerizable composition of the present invention is an antifoaming agent and leveling agent such as silicon and acrylic, UV absorbers such as benzotriazole, benzophenone and salicylic acid, etc., and polymerization inhibition of hydroquinone, hydroquinone monomethyl ether, etc. An agent may be added. These addition amounts are preferably 0.0005 to 5 parts by mass based on 100 parts by mass of the radical polymerizable compound.

The radical polymerizable composition of the present invention includes fillers such as barium sulfate, silicon oxide, talc, mica, kaolin clay, and calcium carbonate, and pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black, and iron oxide. Further, a thixotropic agent such as silica powder such as asbestos, sepiolite, and aerosil may be added. The amount of these fillers is preferably 1000 parts by mass or less, more preferably 1 to 700 parts by mass, based on 100 parts by mass of the radical polymerizable compound. The pigment is preferably 50 parts by mass or less, and more preferably 0.1 to 20 parts by mass. The thixotropic agent is preferably 10 parts by mass or less, and more preferably 0.01 to 5 parts by mass. These are preferably blended immediately before or immediately after mixing the main agent and auxiliary agent in consideration of the storage stability of the radically polymerizable composition.
The radically polymerizable composition to which the color pigment is added can be suitably used particularly as a paint or a flooring agent.

The radical polymerizable composition of the present invention may be one to which various aggregates are added. Natural aggregates include sand, stones, rocks and other minerals that have been crushed, and those that have been colored. Artificial aggregates are artificially processed industrial waste, glass beads, glass bottles and glass. Plated products can also be used. The particle diameter of the aggregate may be selected according to the purpose, but is preferably 0.3 to 10 mm in consideration of workability, surface smoothness of the cured product, and the like. The shape of the aggregate may be any shape such as a circle, a flat shape, an ellipse, a triangle, or a polygon, and may be uniform or non-uniform. These addition amounts are preferably 1000 parts by mass or less, more preferably 1-1000 parts by mass based on 100 parts by mass of the radical polymerizable compound.
The radically polymerizable composition to which the aggregate is added can be suitably used particularly as a road pavement material and a road repair material.

The radically polymerizable composition can be cured by forming a film using a roller, a rake, a trowel, a spray or the like. Moreover, it can be hardened by pouring or filling using a caulking gun, a spatula, a spatula, a trowel or the like.
The composition applied as described above becomes a cured product by curing at room temperature for several hours to several days.

  Production examples, examples and comparative examples will be shown to describe the present invention more specifically. In the following description, parts and% are based on mass.

(Production Example 1)
The solvent diethylene glycol monoethyl ether was filled in a pressure-resistant reactor having a capacity of 300 ml equipped with a stirrer and a temperature controller.
Cyclohexyl acrylate 50 parts Monomer mixture 1 consisting of 30 parts of butyl acrylate, 20 parts of glycidyl methacrylate, 0.2 part of di-t-butyl peroxide, and 30 parts of methyl ethyl ketone is supplied at a constant feed rate (22 g / min, residence time). At 12 minutes, continuous supply from the raw material tank to the reactor was started, and a reaction product corresponding to the supply amount of the monomer mixture 1 was continuously withdrawn from the outlet. After the reaction temperature once decreased immediately after the start of the reaction, a temperature increase due to the heat of polymerization was observed, but the reaction temperature was maintained at 229 to 231 ° C. by controlling the heater. The time when the temperature of the monomer mixture 1 is stabilized after the start of supply is taken as the starting point for collecting the reaction liquid, and after continuing to collect the reaction liquid for 60 minutes, unreacted monomers and the like are continuously removed under reduced pressure. A concentrated liquid (vinyl polymer 1) was obtained. As a result of GC analysis, the unreacted monomer in the concentrate was below the lower limit of detection. The vinyl polymer 1 has a number average molecular weight (Mn) of 1560, a weight average molecular weight (Mw) of 2560, a molecular weight distribution (Mw / Mn) of 1.7, and an epoxy equivalent of 1.32 meq / g (in 1 g of sample). 1.32 milliequivalents of epoxy groups were present). Next, to 54 parts of vinyl polymer 1, 40 parts of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., funkryl FA512MT), 0.5 parts of tetra-n-butylammonium bromide and 0.02 part of hydroquinone are added, and 5% oxygen is added. The temperature was raised to 80 ° C. while blowing nitrogen gas containing. While stirring there, 5.8 parts of methacrylic acid was continuously dropped over about 1 hour, heated to 90 ° C. and kept as it was, and reacted for 12 hours to produce a reaction liquid 1.
55 parts of reaction solution 1, 40 parts of dicyclopentenyloxyethyl methacrylate, 10 parts of trimethylolpropane triacrylate, 0.5 part of paraffin wax having a melting point of 62 ° C., 0.5 part of paraffin wax having a melting point of 46 ° C., N, N— A polymerizable mixture 1 was prepared by mixing 1 part of di (β-hydroxyethyl) -p-toluidine.

(Production Example 2)
A monomer mixture 2 was prepared by mixing 60 parts of methyl methacrylate and 40 parts of n-butyl methacrylate. A flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen substitution and a stirrer was charged with 40 parts of the monomer mixture 2 and 60 parts of methyl ethyl ketone, and heated to 78 ° C. with stirring. Thereto, a mixture of 60 parts of monomer mixture 2 and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over about 3 hours. After completion of the dropwise addition, the mixture was further reacted for 2 hours. The resulting reaction solution was concentrated under reduced pressure, precipitated in methanol, dried and purified to obtain a polymer 2.
The number average molecular weight of the obtained polymer 2 was about 28,000, and the weight average molecular weight was about 80,000. Next, 30 parts of polymer 2, 50 parts of methyl methacrylate, 20 parts of 2-ethylhexyl acrylate, 1 part of paraffin wax having a melting point of 62 ° C. and 1 part of dimethyl P-toluidine are heated to 80 ° C., dissolved and polymerized. Sex mixture 2 was prepared.

(Production Example 3)
A flask equipped with a reflux tube, a stirrer, a nitrogen gas introduction tube, and a thermometer was charged with 23 parts of propylene glycol, 22.2 parts of diethylene glycol, 27.5 parts of phthalic anhydride, and 27.3 parts of maleic anhydride, and nitrogen gas was supplied. While blowing, it was slowly heated to 150 ° C. in an oil bath. The temperature was further raised to 220 ° C. over 4 hours, and the reaction solution 3 was obtained by heating for 6 hours. The acid value of the obtained reaction solution 3 was 28 mgKOH / g.
The reaction mixture 3 at 120 ° C. was dissolved in 60 parts of styrene in which 0.006 part of hydroquinone was dissolved to prepare a polymerizable mixture 3.

Example 1
100 parts of the polymerizable mixture 1, 2 parts of polyphenone CH (manufactured by Mitsui Norin Co., Ltd.), which is tea catechin, and 1 part of cobalt naphthenate 8% (manufactured by Nippon Kagaku Sangyo) were mixed and stirred. Thereto, 2 parts of Nyper NS (containing 40% benzoyl peroxide, manufactured by Nippon Oil & Fats Co., Ltd.) was added as an oxidizing agent, and the mixture was sufficiently stirred to prepare a radical polymerizable composition. Using a stainless steel mold made to have an inner size of 15 cm square, the above composition was applied on an aluminum plate to a thickness of about 1.4 mm, and the surface curability and formaldehyde emission were measured. . The results are shown in Table 1.

The evaluation method is as follows.
(Surface hardening)
An oxidizing agent was added, and the state of the surface portion of the coating film after 2 hours of application was evaluated visually and by touch.
○ It was cured in a non-sticky state on the surface.
Δ: Hardened but sticky on the surface.
X Some unreacted substances remained on the surface.

(Formaldehyde emission)
The obtained coating film was allowed to stand at 23 ° C. for 7 days, and the emission amount of formaldehyde was measured according to JIS K5601-4-1 (analysis of emission component from coating film). Place a crystal dish (120 mm in diameter and 60 mm in height) containing 300 ml of distilled water at the bottom of a desiccator (nominal size 240 mm specified in JIS R3503), and place a stainless steel wire mesh on it to test 15 cm in length and 15 cm in width. Two pieces were placed and allowed to stand for 24 hours, and the diffused formaldehyde was absorbed into distilled water to prepare a sample solution. The formaldehyde concentration in the sample solution was measured by acetylacetone absorptiometry.

(Example 2)
It implemented similarly to Example 1 except having used polyphenon PF (made by Mitsui Norin) instead of polyphenon CH.
(Example 3)
The same procedure as in Example 1 was performed except that the polymerizable mixture 2 was used in place of the polymerizable mixture 1.
Example 4
This was carried out in the same manner as in Example 1 except that the polymerizable mixture 3 was used in place of the polymerizable mixture 1 and that other than Percure VS (manufactured by NOF Corporation) was used as the oxidizing agent in place of Nyper NS.

(Comparative Example 1)
The same operation as in Example 1 was performed except that polyphenone CH was not added in Example 1. Table 2 shows the test results.
(Comparative Example 2)
Example 1 was carried out in the same manner as Example 1 except that 2 parts of urea (special grade reagent manufactured by Kishida Chemical Co., Ltd.) was used instead of polyphenone CH.
(Comparative Example 3)
The same procedure as in Example 1 was performed except that 2 parts of resorcin (manufactured by Sumitomo Chemical Co., Ltd.) were used instead of polyphenone CH in Example 1.
(Comparative Example 4)
The same procedure as in Example 1 was performed except that acetoacetoxyethyl methacrylate (manufactured by Eastman Chemical) was used instead of polyphenone CH in Example 1.
(Comparative Example 5)
The same operation as in Example 3 was performed except that polyphenone CH was not added in Example 3.
(Comparative Example 6)
The same procedure as in Example 3 was performed except that adipic acid dihydrazide (Kishida Chemical reagent grade 1) was used in place of polyphenone CH in Example 3.
(Comparative Example 7)
The same operation as in Example 4 was performed except that polyphenone CH was not added in Example 4.
(Comparative Example 8)
The same procedure as in Example 4 was performed except that hydroxyammonium sulfate was used in place of polyphenone CH in Example 4.

  The radically polymerizable composition of the present invention is useful for applications such as paints, waterproofing materials, flooring materials, road pavement materials, permeable pavement materials, elastic pavement materials, road repair materials, injection materials, or adhesives.

Claims (4)

A radical polymerizable composition containing a radical polymerizable compound, a radical polymerization initiator, and catechin. As a radical polymerizable compound, a polymer A having a functional group A obtained by polymerizing a vinyl monomer at a temperature of 170 ° C. to 350 ° C. and a compound B having a methacryloyl group and a functional group B as raw materials 2. The radical polymerizable composition according to claim 1, comprising a polymer C having a methacryloyl group obtained by reacting the functional group B. 3. The radically polymerizable composition according to claim 1 or 2, which contains dicyclopentenyloxyethyl methacrylate as the radically polymerizable compound. A method for producing a radical polymerization cured product in which the amount of formaldehyde released when radically polymerizing the composition is reduced, wherein the composition according to any one of claims 1 to 3 is radically polymerized.