JPS63182314A - Syrup composition - Google Patents

Abstract

PURPOSE:To obtain a syrup composition which can give a crosslinked methacrylic resin excellent in transparency, heat resistance, etc., by mixing a methyl methacrylate-based monomer and a polymer based on this monomer with a specified polyfunctional monomer at a specified weight ratio. CONSTITUTION:A methyl methacrylate-based monoethylenically unsaturated monomer (A), a polymer (B) formed from a methyl methacrylate-based monomer and a polyfunctional monomer (C) of formula I or II (wherein n is 1-5, A is hydroxyl, a 3-8C hydrocarbon group or the like and m is 3-4) are mixed so that the ratio x (wt.%) of component C to the sum of components A, B and C and the ratio y (wt.%) of component B to the sum of components A and B any lie within the closed region formed by joining points (2, 2), (2, 30), (7, 30), (10, 10), (20, 4), (50, 4), (50, 2) and (2, 2) in the given order in the x-y diagram.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a silica composition for crosslinked methacrylic resin. More specifically, the present invention relates to a silica composition suitable for producing a crosslinked methacrylic resin having excellent transparency and heat resistance.

(Prior art) In general, methacrylic resins whose main component is methyl methacrylate are used in various fields such as lighting covers, automatic Φ parts, right panels, ornaments, and miscellaneous shade shades due to their excellent weather resistance and outstanding transparency. However, since the methacrylic resin is a linear polymer, it has the drawback of insufficient heat resistance, solvent resistance, impact resistance, and surface hardness. For example, the limit of heat resistance is about 100°C, and the current situation is that it is not possible to sufficiently meet the demands of various fields that require heat resistance.

Conventionally, with the aim of improving the heat resistance of methacrylic resins, methods have been developed in which methyl methacrylate and α-methylstyrene are copolymerized (U.S. Pat. No. 3,135°723N), and methyl methacrylate, α-methylstyrene, and maleic anhydride are copolymerized. method (Special Publication No. 45-31.953,
A number of methods have been proposed, including a method of copolymerizing methyl methacrylate, α-methylstyrene and maleimide (Japanese Patent Publication No. 48-95.490).

However, although all of these methods improve heat resistance, the polymerization rate is extremely slow, the polymerization rate does not reach the upper limit, and a high polymerization rate cannot be obtained, and the polymerization rate cannot be obtained efficiently in a relatively short time. Even if it can be obtained, it has both advantages and disadvantages, such as the strong discoloration of the polymer and decreased transparency, weather resistance, surface hardness, mechanical strength, etc., making industrial production extremely difficult, and currently it has not been put into practical use. be.

On the other hand, if a crosslinked structure is generally introduced into a linear polymer, it is easy to think that the above-mentioned drawbacks in heat resistance, solvent resistance, etc. can be improved, and the aim is to be achieved by creating a crosslinked polymer. It is well known that many attempts have been made.

In general, methacrylic resin is a raw material 1ffi or a partial polymer thereof (hereinafter referred to as shirub).
Also includes those dissolved in Form II. ) is produced by polymerizing it in a mold, etc. However, since the 1lffi substance has a low viscosity, it easily leaks from the mold, and even if a degassing operation is performed prior to polymerization, oxygen will dissolve again when it comes into contact with air. Because of the many inconveniences and inconveniences in handling, such as the fact that it is easy to mix, Shirabu, which has a high viscosity, is usually used as a raw material. Because it already contains a portion of the polymer, Shirabu is advantageous in that it takes less time to polymerize than monomers. In this case, a crosslinking agent for introducing crosslinking bonds will be added to this sill. This means that the cross-linking agent is 1
This is because if the mixture is mixed for 11 hours and then partially polymerized, a crosslinked polymer is generated and tends to lose fluidity, making subsequent handling difficult.

On the other hand, different types of uncoupled substances are generally incompatible, except for special exceptions, and when they coexist in a mixed state, macroscopic or microscopic phase separation occurs. Therefore, when two or more polymers with different refractive indexes are mixed, even though they are transparent individually, light is reflected at the interface between the separated phases.
It is well known that this can result in dispersion and, as a result, loss of transparency.

(Problems to be Solved by the Invention) Therefore, a syllabary consisting of a monoethylene unsaturated III ffi form containing methyl methacrylate as the main component (a) and a polymer (b) containing methyl methacrylate as the main IIi fi form component. polyfunctionality 11 as a crosslinking agent
When polymerizing by adding the 'lφ form (C), the polymer (b) that was present in the sagi and the newly generated monomer (a)
The above relationship also applies between the monomer (C) and the polymer made of the monomer (C), and a transparent crosslinked resin cannot necessarily be obtained.

Therefore, the object of the present invention is to develop novel cross-linked methacryl 4
! An object of the present invention is to provide a composition for use as a syringe. Another object of the present invention is to provide a silica composition suitable for producing a crosslinked methacrylic resin having excellent transparency and heat resistance.

(Means for solving the problems) The purpose of these developments is to produce a monoethylenically unsaturated l1ffi product containing methyl methacrylate as the main component (a), and a polymer containing methyl methacrylate as the main monomer component (b).
) and the following general formulas (I), (II) (in formula (I), n
represents an integer of 1 to 5, and in formula (ff), A is a hydrocarbon group having 3 to 8 carbon atoms which may be substituted with water MW or halogen, and m represents 3 or 4. One type of polyfunctional n'ta body (C)
The monoethylenically unsaturated IL1 body (a),
The ratio X (wt%) of the polyfunctional monomer (C) to the total of the polymer (b) and the polyfunctional monomer (C)
), and the ratio y (% of Φ) of the if-described small coalescence (b) to the total of the monoethylenically unsaturated single substance (a) and the small coalescence (b) is the point ( 2,2),
(2,30), (7°30>, (10,10>, (20
, 4) (50°4), <50.2>, and (2,2) are connected in this order to form a closed region, and the crosslinking has excellent transparency and heat resistance. This is achieved by using a silica composition suitable for producing methacrylic resin.

(Function) In the present invention, the monoethylenically unsaturated monomer (a) containing methyl methacrylate as a main component is methyl methacrylate alone or methyl methacrylate and α which can be copolymerized with this.

There is a mixture with β-ethylenically nonvesicular dangling bodies.

In the case of such a suspension mixture, it is desirable that the content of methyl methacrylate be 50 mol% or more, and 60 mol% or more.
It is preferable that it is mol% or more.

The copolymerized hanging body may contain alkyl methacrylates other than methyl methacrylate (for example, ethyl methacrylate, butyl methacrylate,
2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, etc.), methyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, and other alkyl acrylates, 2-hydroxyethyl acrylate , 2-hydroxyalkyl acrylates such as 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 2-hydroxy-3-chloropropyl acrylate;
Hydroxyalkyl methacrylates such as hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, acrylic acid, methacrylic acid, neodymium (meth)acrylate, (meth)acrylic M lead, (meth)acrylic acid Examples include (meth)acrylates such as boron, vinyl chloride, vinyl acetate, (meth)acrylonitrile, (meth)acrylamide, styrene, α-methylstyrene, vinyltoluene, and maleic anhydride.

Mainly methyl methacrylate used in the present invention! 1
The small aggregate (b) having 1 ffi component has an average molecular weight of about I x 10' to 8 x 106, preferably about 5 x 10
~5X10.

Multifunctional tts used as crosslinking agent in the present invention
! 1! The compound (C) is at least one compound represented by the general formula (1) or (II), and specific examples thereof include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyoxy Examples include polyethylene glycol dimethacrylate having 5 repeating units of ethylene, trimethylolethane trimethacrylate, trimethylolethane trimethacrylate, tetramethylolmethane trimethacrylate, and tetramethylolmethanetetramethacrylate.

In the present invention, the monoethylenic vesicles have a
), the polymer (b) and the polyfunctional ttlff1
The ratio of the polyfunctional single substance (C) to the total body is X(!
! 1ffi%) and the monoethylenically unsaturated monomer (a)
And the ratio y (wt%) of the hand coalescence (b) to the total of the polymer (b) is the point (2, 2
), (2,30>, (7°30), (10,10), (
20,4>, (50°4), (50,2), (2,2>
The sword inside the closed region formed by connecting in this order,
The methacrylic resin molded product obtained by combining these silica compositions has extremely good transparency and excellent heat resistance. In particular, when the crosslinking agent is a polyfunctional Qlffi compound represented by the general formula (I>), among the homologues with different 0, only the silica composition within the range shown in the present application has improved heat resistance and excellent It is possible to obtain a heat-resistant methacrylic 1'l Iff molded product.If X is less than 2, the effect of introducing crosslinking will not be sufficient, and if X exceeds 50, the crosslinking density will become excessive, which will cause If y is less than 2, the viscosity of the silica composition will not be sufficient and the above-mentioned advantages expected when using yi will not be exhibited, and if y is more than 30, the silica composition will not have sufficient viscosity, and if y is more than 30, the silica composition will not have sufficient viscosity. Since the combined content is high, it becomes difficult to handle when serving in a boiling stand.

The silica composition thus obtained is polymerized in the presence of a synergistic initiator. This polymerization reaction is carried out at 10° to 150°
℃, preferably at a temperature of 25° to 130°C.

The Φ initiator is usually 0.0% of the above-mentioned silica composition.
01-2% by weight, preferably 0.001-0.5ff!
Hanging% is used. Typical polymerization initiators include lauroyl peroxide, t-butylperoxyisopropyl carbonate, benzoyl peroxide, dicumyl peroxide, t-butylperoxyacetate, and t-butylperoxyisopropyl carbonate.
-butyl peroxybenzoate, di-t-butyl peroxide, azobisisobutyronitrile, etc.

(Example) Next, the present invention will be described in further detail by giving examples. In addition, in the following examples, "part" means a heavy product unless otherwise specified.

In addition, the total light transmission rate and haze are based on JIS K71.
Measurements were made at room temperature in accordance with 05. Heat distortion temperature is JIS
Measured in accordance with K 7207 (bending stress 18.6N9/ci).

Examples 1 to 4 A polyfunctional monomer (C) was dissolved and mixed in a methyl methacrylate solution of polymethyl methacrylate obtained by preliminarily combining methyl methacrylate to obtain a silica composition shown in Table 1. 0.1 per 100 parts of this Shirabu composition
of t-butyl peroxyisobutyrate was added and dissolved, and poured into a commercial casting cell made of two pieces of tempered glass with a gasket of soft 11 vinyl chloride, and heated to 60°C for 3.
After polymerizing for 5 hours, at 70°C for 2 hours, and at 120°C for 2 hours, the polymers were taken out and a transparent plate-like polymer with a thickness of 5M was sealed. The total light IIa transmission rate, haze, and degree of thermal deformation FjA of these plate-like hollow-containing bodies were measured, and the results shown in Table 1 were obtained.

Margin Comparative Examples 1 to 2 Below, Silk compositions shown in Table 2 were obtained in the same manner as Examples 1 to 4. 0.1 part of t-per 100 parts of this syrup composition
Butyl peroxyisobutyrate was added and dissolved, and polymerization was carried out in the same manner as in Examples 1 to 4 to obtain a plate-shaped polymer having a thickness of 5 ml. The total light transmittance, haze and heat distortion temperature of this material were measured, and the bundles shown in Table 2 were made.

Table 2 Comparative Example 3 0.1 part of t-butylperoxyisobutyrate was added and dissolved per 100 parts of methyl methacrylate, and Examples 1-
Polymerization was carried out in the same manner as in 4 to obtain a plate-like polymer having a thickness of 5 mm. The total light transmittance of this product is 93.0%, and the haze is 0.
．． 2%, and the heat distortion temperature was 101°C.

Example 5 Medium 1 body consisting of methyl methacrylate and styrene (a)
(Sprene/methyl methacrylate ffl ratio 2/98
), methyl methacrylate-methyl acrylate covalent union (b) [methyl acrylate/methyl methacrylate Φ ratio 6/94] with an average molecular weight of 1.2×105 was added to y=
Ethylene glycol dimethacrylate was mixed and dissolved in the solution obtained by dissolving x=8 in a ratio of x=10.

Examples 1 to 4
Polymerization was carried out in the same manner as above to obtain a transparent plate-like polymer having a thickness of 5 ms+. The total light transmittance of this material was 90.7%, the haze was 1.6%, and the heat distortion temperature was 118°C.

Example 6 Polymethyl methacrylate 3 with an average molecular weight FIA of 7.0×10 obtained by prepolymerizing methyl methacrylate
15 parts of ethylene glycol dimethacrylate, 1.4 (8
)-P-Menthagene 0゜01 parts, 2.2'Azobis(
4-Methoxy-2゜4-dimethylvaleronitrile) 0.
0.003 parts of di-t-butyl peroxide and 0.3 parts of di-t-butyl peroxide were dissolved and mixed, poured into the same cast polymerization cell as in Examples 1 to 4, polymerized at 50°C for 3 hours, and taken out to form a gel-like polymer. Obtained union. This gel-like aggregate was press-molded using a mold that could accommodate a flat plate of 15 υ square and 5 M thick. Mold temperature 130
After holding the mold at a maximum pressure of 65 kg/cII for 15 minutes at 120° C., the mold was cooled to 120° C. and taken out to obtain a transparent plate-shaped hand assembly. All the light of this plate polymer #! The transmittance is 90.2%,
The haze was 2.1% and the heat distortion temperature was 125°C.

(Effects of the Invention) As described above, the present invention provides monoethylenic vesicle monomers containing methyl methacrylate as a main component, polymers containing methyl methacrylate as a monomer component, and general formula (I). , (II), and the amount of the polyfunctional Ql in the total of the monoethylenically unsaturated monomer, the hand-combined monomer, and the polyfunctional monomer; A sillage characterized in that the proportion X of the monoethylenic vesicles and the proportion y of the polymer in the total of the monoethylenic vesicles and the polymer are within a closed region formed by an X-y dust mark. Since it is a composition, it is possible to control a methacrylic resin molded product having extremely good transparency and excellent heat resistance by using this composition. Therefore, according to the present invention, it is possible to provide synthetic resin molded products such as covers for headlamps that require heat resistance, glazing for automobiles such as tail lamps, and covers for water heaters that utilize solar energy.

[Brief explanation of the drawing]

The drawing shows the ratio of polyfunctional bamboo middle body × (φ hanging %) and the polymer ratio y (ff'
1ffi%) is a 1JX-y coordinate diagram. Patent applicant: Kyowa Gas Chemical Industry Co., Ltd. Figure 1, x (f amount%)

Claims (3)

[Claims] (1) Monoethylenically unsaturated monomer (a) containing methyl methacrylate as the main component, polymer (b) containing methyl methacrylate as the main monomer component, and the following general formulas (I) and (II) ▲ Formula , chemical formulas, tables, etc.▼(
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In formula (I), n represents an integer from 1 to 5, and formula (II)
wherein A is a hydrocarbon group having 3 to 8 carbon atoms which may be substituted with a hydroxyl group or a halogen, and m represents 3 or 4. , the ratio X (by weight) of the polyfunctional monomer (c) to the total of the monoethylenically unsaturated monomer (a), the polymer (b), and the polyfunctional monomer (c) %)and,
The monoethylenically unsaturated monomer (a) and the polymer (
The ratio y (wt%) of the polymer (b) to the total of b)
) is the point (2.2), (2, 30
), (7, 30), (10, 10), (20, 4) (5
Production of a crosslinked methacrylic resin having excellent transparency and heat resistance, characterized by being inside a closed region formed by connecting 0, 4), (50, 2), and (2, 2) in this order. Syrup composition suitable for. (2) The syrup composition according to claim 1, wherein the polyfunctional monomer is represented by the general formula (I). (3) The syrup composition according to claim 1, wherein the polyfunctional monomer is represented by the general formula (II).