JPS6240370B2 - - Google Patents

Description

[Detailed description of the invention]

The syrup whose main ingredient is methyl methacrylate is made of glass fiber reinforced board, one kitchen counter,
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 harsh conditions of use, such as prolonged immersion in boiling water, when filled with a filler such as alumina, the molded product has the disadvantage of whitening, peeling, 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 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 9% by weight of one or more monomers selected from acrylic esters, polyvalent (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); (B) (d) having a glycidyl group and at least 1
Monomers 3 to 97 copolymerizable with methyl methacrylate having 3 or more ethylenically unsaturated bonds
(e) A monomer copolymerizable with methyl methacrylate that has no reactivity with methyl methacrylate monomers and/or glycidyl groups and has at least one ethylenically unsaturated bond, Aromatic vinyl monomer, (meth)
A mixture of 97 to 3% by weight of one or more monomers selected from acrylic esters, polyvalent (meth)acrylic esters, and fumaric esters (however, monomer (d) and monomer The total of the body (e) is
A methyl methacrylate syrup composition prepared by mixing 99 to 1 part by weight of syrup (B) copolymerized with 10 to 60 parts by weight of (100% by weight) to a total of 100 parts by weight It is something to do. The present invention will be explained in detail below. Note that parts and percentages hereinafter 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 (B) 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 monomers, (meth)acrylic acid esters, polyvalent (meth) acrylic 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. The content of monomers in the syrup (B) that can be copolymerized with methyl methacrylate having a (d)glycidyl group and having at least one ethylenically unsaturated bond is required to be 3 to 97%. This is 3%
If it is less than 97%, the water resistance of the molded product will be poor, and if it exceeds 97%, the storage stability of the syrup composition after mixing with syrup (A) will be poor, and the increase in viscosity over time during storage will be extremely large. Among the monomers (b) in the syrup (A) of the present invention, (i) carboxyl group-containing monomers include, for example, methacrylic acid, maleic anhydride, maleic acid,
fumaric acid, acrylic acid, etc. (ii) Hydroxyl group-containing monomers include, for example, 2-hydroxyethyl methacrylate, neopentyl glycol monomethacrylate, trimethylolpropane monomethacrylate, trimethylolpropane dimethacrylate, polyethylene glycol monomethacrylate, 2-hydroxyethyl acrylate, neopentyl glycol monoacrylate, trimethylolpropane monoacrylate, trimethylolpropane diacrylate, polyethylene glycol monoacrylate, etc. (iii) As the phosphate group-containing monomer, for example, 2-hydroxydoethyl methacrylate orthophosphoric acid ester of , phosphite of 2-hydroxyethyl methacrylate, orthophosphoric acid ester of 2-hydroxyethyl acrylate, phosphite of 2-hydroxyethyl acrylate, etc., and (iv) amino group-containing monomer For example, N
-Methylaminoethyl methacrylate, 4-N-
Methylaminocyclohexyl methacrylate,
N,N-dimethylaminoethyl methacrylate,
methacrylamide, crotonic acid amide, vinylamine, N-ethylvinylamine, allylamine,
diallylamine, N-methylallylamine, N-
Methylaminoethyl acrylate, 4-N-methylaminocyclohexyl acrylate, N,N-
Specific examples include dimethylaminoethyl acrylate and acrylamide, and one or more of these monomers may be used. Examples of the monomer (c) in the syrup (A) of the present invention include styrene, 2-methylstyrene,
Aromatic vinyl monomers such as chlorostyrene, t-butylstyrene, divinylbenzene, such as ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate etc. (meta)
Acrylic esters such as ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, etc. Examples include monomers such as polyvalent (meth)acrylic acid esters, such as fumaric acid esters such as butyl fumaric acid ester. In the present invention, monomers having a glycidyl group in the syrup (B) and copolymerizable with methyl methacrylate having at least one ethylenically unsaturated bond include, for example, glycidyl methacrylate, β-methylglycidyl methacrylate, N −
Glycidyl methacrylamide, methacrylic acid adduct of epoxy resin consisting of polyvalent phenol and epihalohydrin, glycidyl acrylate, β-methylglycidyl acrylate, N-glycidyl acrylamide, acrylic acid adduct of epoxy resin consisting of polyvalent phenol and epihalohydrin, allylglycidyl One or more of these monomers, including monomers such as ether, are used. Monomers copolymerizable with methyl methacrylate that are not reactive with the glycidyl group in (e) of the syrup (B) and have at least one ethylenically unsaturated bond are aromatic vinyl monomers, ( Meta)
One or more kinds of compounds selected from acrylic esters, polyvalent (meth)acrylic esters, and fumaric esters, and specifically, those exemplified in (c) above can be exemplified as they are. Both the syrup (A) and the syrup (B) are prepared by stirring and mixing the above-mentioned monomer mixtures in a reaction tank equipped with stirring and heating/cooling equipment. Peroxyneodecanoate, t-butylperoxypivalate, t-butylperoxy-2-
Using a catalyst such as ethylhexanoate and a chain transfer agent such as t-dodecyl mercaptan, n-dodecyl mercaptan, thioglycolic acid, or mercaptoethanol, the reaction is carried out at a temperature of 50°C to 110°C for 3 to 24 hours to achieve a 10 to 60% Each is obtained by polymerization. If the polymerization rate is less than 10%, the water resistance of the molded product will be poor, and if it exceeds 60%, the syrup will have a high viscosity and workability will be extremely poor. The methyl methacrylate syrup composition of the present invention is the syrup (A) 1 obtained as described above.
It is obtained by mixing ~99 parts and 99~1 part of syrup (B) for 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 (B) 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 100% of the molding mixture is injected into a mold whose inner surface has been coated with a release agent such as silicone or polyvinyl alcohol, or onto a release paper such as polyester film or cellophane paper, and then heated at a temperature of 40 to 40°C. It may be hardened and molded at 120°C for about 20 to 200 minutes. Embodiments of the present invention will be specifically explained below with reference to 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, including the following production examples, was determined from the refractive index using an Atsube refractometer. Methyl methacrylate 70.0 parts Styrene 25.0 parts Trimethylolpropane 3.0 parts Trimethacrylate Methacrylic acid 1.6 parts t-Dodecylmercaptan 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 3.0 parts N-methylaminoethyl dimethacrylate 1.6 parts t-dodecyl mercaptan methacrylate 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 1.0 parts Trimethacrylate 2-hydroxyethyl 15.0 parts Methacrylate 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 Trimethylolpropane 1.0 parts Trimethacrylate 2-hydroxyethyl methacrylate 5.0 parts Orthophosphoric acid ester n-dodecyl mercaptan 0.1 part Azobisisobutyronitrile 0.3 parts Total 100.0 parts Production example 5 ( Production of syrup (B)) 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 10 hours, polymerization rate 38%, viscosity
A syrup (B-1) of 680 centipoise was obtained. Methyl methacrylate 54.5 parts Styrene 23.0 parts Glycidyl methacrylate 20.0 parts Trimethylolpropane 2.0 parts Trimethacrylate t-dodecyl mercaptan 0.2 parts Azobisisobutyronitrile 0.3 parts Total 100.0 parts Production Example 6 (Production of syrup (B)) 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 9 hours, polymerization rate 35%, viscosity
A syrup (B-2) of 590 centipoise was obtained. Methyl methacrylate: 60.0 parts Styrene: 25.0 parts Production of syrup (D)) In the same flask as in Production Example 1, add the monomer of Production Example 4 in which 5.0 parts of orthophosphoric acid ester of 2-hydroxyethyl methacrylate was replaced with methyl methacrylate, and a polymerization initiator. and a chain transfer agent were charged and 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 95.0 parts Trimethylolpropane 1.0 parts Trimethacrylate Butyl fumarate 3.6 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 1 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 the composition was reacted at 103 to 107°C for 1 hour to obtain 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, 20.0 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 chain transfer agent with 18.5 parts replaced with methyl methacrylate was charged and reacted at 103 to 107°C for 6 hours to obtain a syrup (D-
3) was obtained. Methyl methacrylate 73.0 parts Styrene 23.0 parts Glycidyl methacrylate 1.5 parts Trimethylolpropane 2.0 parts Trimethacrylate t-dodecylmercaptan 0.2 parts Azobisisobutyronitrile 0.3 parts Total 100.0 parts Examples 1 to 8 In the production examples 1 to 6 described above. The obtained syrup was cured under the conditions shown in Table 1 to obtain a transparent molded product.
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 as shown in Table 3, 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 3. A molded product with a glossy surface was obtained. 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); (B) (d) having a glycidyl group and at least 1
Monomers 3 to 97 copolymerizable with methyl methacrylate having 3 or more ethylenically unsaturated bonds
(e) A monomer copolymerizable with methyl methacrylate that has no reactivity with methyl methacrylate monomers and/or glycidyl groups and has at least one ethylenically unsaturated bond, Aromatic vinyl monomer, (meth)
A mixture of 97 to 3% by weight of one or more monomers selected from acrylic esters, polyvalent (meth)acrylic esters, and fumaric esters (however, monomer (d) and monomer The total of the body (e) is
A methyl methacrylate syrup composition prepared by mixing 99 to 1 part by weight of syrup (B), which is a copolymerized 10 to 60% by weight of 100% by weight), to a total of 100 parts by weight.