JPS6240369B2 - - Google Patents

Description

[Detailed description of the invention]

The syrup whose main ingredient is methyl methacrylate can be used for glass fiber reinforced boards, kitchen countertops,
It is used for molding things such as washstands, and has excellent weather resistance, such as preventing molded products from yellowing. However, glass fiber, silica sand,
Under severe usage conditions such as prolonged immersion in boiling water while filled with a filler such as alumina, the molded product has the disadvantage of whitening, matting, etc. The present inventors mixed a syrup containing a functional group reactive with a glycidyl group and a syrup containing a glycidyl group in a tank equipped with a stirrer, and mixed benzoyl peroxide, azobisisobutyronitrile, t - Radical polymerization is carried out using a catalyst such as butylperoxyneodecanoate, t-butylperoxypivalate, or t-butylperoxy-2-ethylhexanoate, and glycidyl groups and glycidyl groups and reactive By concurrently carrying out an addition reaction with a certain functional group, we succeeded in dramatically improving water resistance under harsh conditions. That is, the present invention comprises: (A) (i) 5 to 95% by weight of methyl methacrylate monomer; (b) methyl methacrylate that is reactive with glycidyl groups and has at least one ethylenically unsaturated bond; A monomer copolymerizable with (i) a carboxyl group-containing monomer,
(ii) 95 to 1% by weight of one or more monomers selected from hydroxyl group-containing monomers, (iii) phosphate group-containing monomers, and (iv) amino group-containing monomers;
and (c) an aromatic vinyl monomer, (meth) which is not reactive with glycidyl groups and is copolymerizable with methyl methacrylate having at least one ethylenically unsaturated bond.
A mixture of 0 to 94% by weight of one or more monomers selected from acrylic esters, poly(meth)acrylic esters, and fumaric esters (however, monomer (a) and monomer (b) and monomer (c)
total is 100% by weight) 10~60% by weight
1 to 99 parts by weight of the copolymerized syrup (A); (C) (d) 3 to 97 parts by weight of a monomer having a glycidyl group and other copolymerizable (meth)acrylic esters and fumaric esters; , a (meth)acrylic copolymer having a glycidyl group and having a number average molecular weight of 1,500 to 50,000, copolymerized with 97 to 3% by weight of one or more monomers selected from aromatic vinyl monomers. 5 to 95% by weight of (e) methyl methacrylate monomer and/or aromatic vinyl monomer copolymerizable with methyl methacrylate having at least one ethylenically unsaturated bond, (meth)acrylic acid ester , polyhydric (meth)acrylic acid ester, fumaric acid ester, and hydroxyl group-containing monomer.
~1 part by weight; A methyl methacrylate syrup composition is prepared by mixing 1 part by weight in total to 100 parts by weight. The present invention will be explained in detail below. Note that in the following, % and parts are based on weight unless otherwise specified. The content of (a) methyl methacrylate monomer in the syrup (A) must be in the range of 5 to 95%.
If it is less than 5%, the storage stability of the syrup composition after mixing with the syrup (C) will be poor, and the increase in viscosity over time during storage will be extremely large. Also, 95%
If it exceeds this, the water resistance of the molded product will deteriorate. On the other hand, (b)
A monomer that is reactive with a glycidyl group and copolymerizable with methyl methacrylate having at least one ethylenically unsaturated bond, comprising (i) a carboxyl group-containing monomer, (ii) a hydroxyl group. 1% or more of one or more monomers selected from the group containing monomers, (iii) phosphate group-containing monomers, and (iv) amino group-containing monomers, and (c) glycidyl groups. Monomers that are non-reactive and copolymerizable with methyl methacrylate having at least one ethylenically unsaturated bond, such as aromatic vinyl compounds, (meth)acrylic acid esters, and polyhydric (meth)acrylic acid. ester,
The content of one or more monomers selected from fumaric acid esters must be 94% or less. If the former (b) is less than 1% or the latter (c) exceeds 94%, the molded product will have poor water resistance. Among the monomers (b) in the present invention, (i) carboxyl group-containing monomers include, for example, methacrylic acid, maleic anhydride, maleic acid, fumaric acid, acrylic acid, and (ii) hydroxyl group-containing monomers. Containing monomers include, for example, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, neopentyl glycol monomethacrylate, trimethylolpropane monomethacrylate, trimethylolpropane dimethacrylate, polyethylene glycol monomethacrylate, 2-hydroxyethyl acrylate, 2-hydroxy Propyl acrylate, neopentyl glycol monoacrylate, trimethylolpropane monoacrylate, trimethylolpropane diacrylate,
polyethylene glycol monoacrylate etc. (iii)
Examples of the phosphate group-containing monomer include orthophosphoric acid ester of 2-hydroxymethyl methacrylate;
Phosphite of 2-hydroxyethyl methacrylate, orthophosphate of 2-hydroxyethyl acrylate, phosphite of 2-hydroxyethyl acrylate, etc., and (iv) amino group-containing monomers include, for example, N- Methylaminoethyl methacrylate, 4-N-methylaminocyclohexyl methacrylate, N,N-dimethylaminoethyl methacrylate, methacrylamide,
Crotonic acid amide, vinylamine, N-ethylvinylamine, allylamine, diallylamine, N
Specific examples include -methylallylamine, N-methylaminoethyl acrylate, 4-N-methylaminocyclohexyl acrylate, N,N-dimethylaminoethyl acrylate, and acrylamide. One or more of these monomers may be used. Examples of the monomer (iii) in the present invention include aromatic vinyl monomers such as styrene, 2-methylstyrene, chlorostyrene, t-butylstyrene, and divinylbenzene; examples include ethyl methacrylate, butyl methacrylate, and 2-methylstyrene; Ethylhexyl methacrylate, lauryl methacrylate, ethyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
(meth)acrylic esters such as lauryl acrylate, such as ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate,
Polyhydric (meth)acrylic acid esters such as trimethalolpropane trimethacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, fumaric acid esters such as butyl fumarate, etc. monomers are mentioned. The syrup (A) is prepared by stirring and mixing a mixture of the above monomers in a reaction tank equipped with stirring and heating/cooling equipment, and then azobisisobutyronitrile, benzoyl peroxide, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-
from 50°C using a catalyst such as butyl peroxy-2-ethylhexanoate and a chain transfer agent such as t-dodecyl mercaptan, n-dodecyl mercaptan, thioglycolic acid, or mercaptoethanol.
It is obtained by reacting at a temperature of 110°C for 3 to 24 hours to achieve a 10 to 60% copolymerization. If the polymerization rate is less than 10%, the water resistance of the molded product will deteriorate, and if it exceeds 60%, the syrup will become highly viscous and workability will deteriorate significantly. In the present invention, the (meth)acrylic copolymer having a (d)glycidyl group in the syrup (C) includes 3 to 97% by weight of a monomer having a glycidyl group and a monomer that can be copolymerized with a monomer having a glycidyl group. One or more monomers selected from (meth)acrylic esters, fumaric esters, and aromatic vinyl monomers
The number average molecular weight is 1500 when copolymerized with 97 to 3 weight
~50000 copolymers are used. As the monomer having a glycidyl group, for example, one or more of glycidyl methacrylate, glycidyl acrylate, β-methylglycidyl methacrylate, β-methylglycidyl acrylate, allyl glycidyl ether, etc. can be used, and monomers having a glycidyl group can be used. Examples of monomers that can be copolymerized with the polymer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
(Meth)acrylic acid esters such as lauryl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate; butyl fumarate, etc. Fumaric acid esters; styrene,
Aromatic vinyl monomers such as α-methylstyrene are used. The monomer having a glycidyl group in the (meth)acrylic copolymer having a glycidyl group must be in the range of 3 to 97%, and if this is less than 3%, the water resistance of the molded product will deteriorate. Moreover, if it exceeds 97%, gel is likely to be generated during polymerization, which is not preferable. It also has a glycidyl group (meta)
The number average molecular weight of acrylic copolymer is 1500-50000
If it is less than 1500, the water resistance of the molded product will be poor, and if it is less than 50000
Exceeding this is not preferable since the viscosity of the syrup increases, resulting in poor workability. In the present invention, the (meth)acrylic polymer (d) having a glycidyl group in the syrup (C) is
48-38617, Japanese Patent Publication No. 52-15090, and the like can be used. For example, expression () (In the formula, R ₁ is H or CH ₃ , R ₃ has 1 to 14 carbon atoms
(representing an alkyl group) and a (meth)acrylic acid ester represented by the formula () In the formula, R ₁ represents H or CH ₃ It may be combined with a vinyl monomer such as methacrylic acid ester or styrene, and the formula () (In the formula, R ₁ and R ₁ represent H or CH ₃ ) (meth)acrylic acid (methyl) glycidyl ester represented by the formula () (In the formula, R ₁ and R ₁ represent H or CH ₃ ) Softening point obtained by copolymerizing with (methyl)glycidyl (meth)allyl ether represented by
Any polymer having a number average molecular weight of 3,000 to 12,000 at ℃ can be used. In addition, in the syrup (C) of the present invention, the monomer (e) for dissolving the (meth)acrylic polymer (d) having a glycidyl group is a methyl methacrylate monomer and/or at least one ethylene selected from aromatic vinyl monomers, (meth)acrylic esters, polyvalent (meth)acrylic esters, fumaric esters, and hydroxyl group-containing monomers that can be copolymerized with methyl methacrylate having sexually unsaturated bonds. Either one type or two or more types of monomers can be used. Specific examples of these include those exemplified in (b) and (c) above. Among these, monomers containing hydroxyl groups are the easiest to use because they are less likely to cause reactions such as thickening over time after dissolving the copolymer. The syrup (C) can be easily obtained by dissolving the above-mentioned (meth)acrylic polymer having a glycidyl group in the above-mentioned monomer having an ethylenically unsaturated bond in a tank equipped with stirring equipment. The methyl methacrylate syrup composition of the present invention is obtained by mixing 1 to 99 parts of the syrup (A) obtained as described above and 99 to 1 part of the syrup (C) to a total of 100 parts. If the amount of syrup (A) is less than 1 part or exceeds 99 parts, the water resistance of the molded product will deteriorate. In order to manufacture a molded article using the syrup composition of the present invention, the following operations may be performed, for example.
That is, syrup (A) and syrup (C) in the above proportions are mixed in a tank equipped with stirring equipment, and azobisisobutyronitrile, benzoyl peroxide, and t-butyl peroxide are added to 100 parts of the resulting syrup composition. 0.1 to 10 parts of a catalyst such as oxyneodecanoate, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, etc., and 10 to 300 parts of a filler such as glass fiber, silica sand, alumina, etc.
The molding mixture obtained by adding and mixing 50% of the molding mixture is injected into a mold whose inner surface has been coated with a mold release agent such as silicone or polyvinyl alcohol, or onto a mold release paper such as polyester film or cellophane paper, and then heated at a temperature of 40°C. It may be hardened and molded at ~120°C for about 20 to 200 minutes. Hereinafter, aspects of the present invention will be specifically explained using production examples and examples. Production Example 1 (Production of syrup (A)) The following composition consisting of a monomer, a polymerization initiator, and a chain transfer agent was charged into a flask equipped with a stirrer.
Reacted at 103-107℃ for 7 hours, polymerization rate 31%, viscosity
A syrup (A-1) of 520 centipoise was obtained. In addition, the polymerization rate was determined from the refractive index using an Atsube refractometer, including the production examples hereinafter. Methyl methacrylate 70.0 parts Styrene 25.0 parts Trimethylolpropane trimethacrylate 3.0 parts Methacrylic acid 1.6 parts t-Dodecyl mercaptan 0.1 part Azobisisobutyronitrile 0.3 parts Total 100.0 parts Production Example 2 (Production of syrup (A)) Production Example 1 The following composition consisting of a monomer, a polymerization initiator, and a chain transfer agent was charged in the same flask,
Reacted at 103-107℃ for 12 hours, polymerization rate 27%, viscosity
A syrup (A-2) of 480 centipoise was obtained. Methyl methacrylate 70.0 parts Styrene 25.0 parts Neopentyl glycol dimethacrylate 3.0 parts N-methylaminoethyl methacrylate 1.6 parts t-dodecyl mercaptan 0.1 parts Azobisisobutyronitrile 0.3 parts Total 100.0 parts Production example 3 (Production of syrup (A)) The following composition consisting of a monomer, a polymerization initiator, and a chain transfer agent was charged into the same flask as in Production Example 1,
Reacted at 103-107℃ for 6 hours, polymerization rate 24%, viscosity
A syrup (A-3) of 430 centipoise was obtained. Methyl methacrylate 75.0 parts Isobutyl methacrylate 8.6 parts Trimethylolpropane Trimethacrylate 1.0 parts 2-Hydroxyethyl methacrylate 15.0 parts n-Dodecyl mercaptan 0.1 parts Azobisisobutyronitrile 0.3 parts Total 100.0 parts Production example 4 (Production of syrup (A)) The following composition consisting of a monomer, a polymerization initiator, and a chain transfer agent was charged into the same flask as in Production Example 1,
Reacted at 100-105℃ for 6 hours, polymerization rate 19%, viscosity
A syrup (A-4) of 920 centipoise was obtained. Methyl methacrylate 90.0 parts Butyl fumarate 3.6 parts Trimethacrylate propane trimethacrylate 1.0 parts Orthophosphoric acid ester of 2-hydroxyethyl methacrylate 5.0 parts n-dodecyl mercaptan 0.1 parts Azobisisobutyronitrile 0.3 parts Total 100.0 parts Production example 5 ( Production of syrup (C)) The following composition consisting of a monomer, a polymerization initiator and a solvent was charged into the same flask as in Production Example 1, and
Polymerization was carried out by heating at 110°C for 8 hours. Next, toluene was distilled off under heating and reduced pressure to obtain a solid methacrylic copolymer having glycidyl groups.
The number average molecular weight of the methacrylic copolymer was 12,000. Methyl methacrylate 25.0 parts Styrene 4.0 parts Glycidyl methacrylate 10.0 parts Benzoyl peroxide 1.0 parts Toluene 60.0 parts Total 100.0 parts 50.0 parts of the above methacrylic copolymer and 50 parts of the following monomers
A syrup (C-1) having a viscosity of 1750 centipoise was obtained. Methyl methacrylate 33.0 parts Styrene 14.0 parts Trimethylolpropane trimethacrylate 3.0 parts Total 50.0 parts Production Example 6 (Production of syrup (C)) In the same flask as in Production Example 1, add the following composition consisting of monomers, polymerization initiator, and solvent. Prepare, 105～
Polymerization was carried out by heating at 110°C for 8 hours. Next, toluene was distilled off under heating and reduced pressure to obtain a solid methacrylic copolymer having glycidyl groups.
The number average molecular weight of the methacrylic copolymer was 10,000. Methyl methacrylate: 20.0 parts Styrene: 5.0 parts , a syrup with a viscosity of 1300 centipoise (C
-2) was obtained. Methyl methacrylate 33.0 parts Styrene 5.0 parts Isobutyl methacrylate 4.0 parts 2-hydroxyethyl methacrylate 3.0 parts Butyl fumarate 2.0 parts Trimethylolpropane trimethacrylate 3.0 parts Total 50.0 parts Production Example 7 (Production of syrup (D) for comparison) Production Example 1 Into the same flask was charged the following composition consisting of the monomers of Production Example 4 in which 5.0 parts of orthophosphoric acid ester of 2-hydroxyethyl methacrylate was replaced with methyl methacrylate, a polymerization initiator, and a chain transfer agent. The mixture was reacted at 100 to 105°C for 6 hours to obtain syrup (D-1) with a polymerization rate of 20% and a viscosity of 870 centipoise. Methyl methacrylate 95. parts Butyl fumarate 3.6 parts Trimethylolpropane trimethacrylate 1.0 parts n-dodecyl mercaptan 0.1 part Azobisisobutyronitrile 0.3 parts Total 100.0 parts Production example 8 (Production of syrup (D) for comparison) Production example A composition consisting of the same monomer, polymerization initiator, and chain transfer agent as in Production Example 1 was charged into the same flask as in Production Example 1, and reacted at 103 to 107°C for 1 hour to form a syrup with a polymerization rate of 5% and a viscosity of 20 centipoise. (D-
2) was obtained. Production Example 9 (Production of syrup (D) for comparison) Into the same flask as in Production Example 1, 10.0 parts of glycidyl methacrylate of the monomers in Production Example 5 was added.
The following composition consisting of a monomer, a polymerization initiator, and a solvent in which 9.3 parts were replaced with methyl methacrylate was charged, and polymerization was carried out by heating at 105 to 110°C for 8 hours. Next, toluene was distilled off under heating and reduced pressure to obtain a solid methacrylic copolymer having glycidyl groups. The number average molecular weight of the methacrylic copolymer was 15,000. Methyl methacrylate 34.3 parts Styrene 4.0 parts Glycidyl methacrylate 0.7 parts Benzoyl peroxide 1.0 parts Toluene 60.0 parts Total 100.0 parts 50.0 parts of the above methacrylic copolymer and 50 parts of the following monomers
A syrup (D-3) having a viscosity of 2300 centipoise was obtained. Methyl methacrylate 33.0 parts Styrene 14.0 parts Trimethylolpropane trimethacrylate 3.0 parts Total 50.0 parts Examples 1 to 8 The syrups obtained in Production Examples 1 to 6 described above were cured under the conditions shown in Table 1 to form transparent molded products. Obtained.
Furthermore, 70 parts of silica sand powder was mixed with 30 parts of the syrup shown in Table 1, poured into a mold made of stainless steel or aluminum coated with a mold release agent such as silicone or polyvinyl alcohol, and cured under the curing conditions shown in Table 1. A molded product with a glossy surface was obtained. Table 2 shows the boiling water resistance of the molded product obtained. As is clear from Table 2, water resistance under severe conditions is dramatically improved by causing an addition reaction between a glycidyl group and a functional group reactive with the glycidyl group during radical polymerization. Comparative Examples 1 to 7 The syrups obtained in the production examples were cured under the conditions shown in Table 3 to obtain transparent molded products. Furthermore, 70 parts of silica sand powder was mixed with 30 parts of the syrup of the composition shown in Table 3, and poured into a mold made of stainless steel, aluminum, etc. coated with a mold release agent such as silicone or polyvinyl alcohol, and cured under the curing conditions shown in Table 3. A molded product having a glossy surface was obtained by curing. Table 4 shows the boiling water resistance of the molded product obtained.

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Claims (1)

[Claims] 1 (A) (a) Methyl methacrylate monomer 5 to 95
(b) A monomer that is reactive with a glycidyl group and copolymerizable with methyl methacrylate having at least one ethylenically unsaturated bond, which contains (i) a carboxyl group-containing monomer; body,
(ii) 95 to 1% by weight of one or more monomers selected from hydroxyl group-containing monomers, (iii) phosphate group-containing monomers, and (iv) amino group-containing monomers;
and (c) an aromatic vinyl monomer, (meth) which is not reactive with glycidyl groups and is copolymerizable with methyl methacrylate having at least one ethylenically unsaturated bond.
A mixture of 0 to 94% by weight of one or more monomers selected from acrylic esters, polyvalent (meth)acrylic esters, and fumaric esters (with the exception of monomer (a) and monomer (b) and monomer (c)
total is 100% by weight) 10~60% by weight
1 to 99 parts by weight of the copolymerized syrup (A); (C) (d) 3 to 97 parts by weight of a monomer having a glycidyl group, and other copolymerizable (meth)acrylic esters and fumaric esters. , a (meth)acrylic copolymer having a glycidyl group and having a number average molecular weight of 1,500 to 50,000 copolymerized with 97 to 3% by weight of one or more monomers selected from aromatic vinyl monomers. 5 to 95% by weight of (e) methyl methacrylate monomer and/or aromatic vinyl monomer copolymerizable with methyl methacrylate having at least one ethylenically unsaturated bond, (meth)acrylic acid ester , polyhydric (meth)acrylic acid ester, fumaric acid ester, and hydroxyl group-containing monomer.
A methyl methacrylate syrup composition comprising: ~1 part by weight; mixed in a total of 100 parts by weight.