JPH1067907A - Resin composition and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition capable of improving a flowing property without deteriorating a transparency and a weatherproof property by using a resin component such as an acrylic resin and a specific aliphatic polyester as indispensable components. SOLUTION: This resin composition contains (A) a resin component of (i) an acrylic resin or (ii) a copolymer resin obtained by polymerizing >=60wt.% acrylic monomer with an aromatic vinyl-based monomer and (B) a reaction product of (iii) an aliphatic dicarboxylic acid with (iv) a diol component and having 50-5000 cps (at 25 deg.C) viscosity measured by a BM type viscometer, as indispensable components. Further, it is preferable to contain in a ratio of 0.1-20wt.% component (B) based on the component (A). Thus, it is possible to improve flowing properties of an acrylic resin, a MS resin or rubber-modified resins of them without deteriorating a transparency and a weatherproof property, and also an oil resistance of the formed product is excellent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an improved acrylic resin or a copolymer resin obtained by polymerizing an acrylic monomer with an aromatic vinyl monomer at a ratio of 60% by weight or more, and a specific compound. For a resin composition and a method for producing the same,
More specifically, an aliphatic dicarboxylic acid and a diol component are added to a resin component containing an acrylic resin or a copolymer resin obtained by polymerizing an acrylic monomer with an aromatic vinyl monomer in a proportion of 60% by weight or more. , A resin composition having excellent transparency, weatherability and practical strength obtained by containing an aliphatic polyester having a specific structure obtained by reacting The present invention relates to a product and a method for manufacturing the same.

[0002]

2. Description of the Related Art Acrylic resin and MS resin, which is a styrene-methyl methacrylate copolymer, are transparent, have excellent strength and weather resistance, and are used as molding materials for signboards, nameplates, carport roofing materials, lighting and projection televisions. It is used for applications such as display. In addition, acrylic resin and MS resin generally have a weak impact strength and have a drawback that their use is limited. Therefore, as a resin having improved impact strength of acrylic resin or MS resin, acrylic rubber or butadiene rubber is used. An impact-resistant acrylic resin obtained by graft polymerization of an alkyl (meth) acrylate is known.

[0003] Since such an acrylic resin or an MS resin containing a large amount of MMA component has poor fluidity, moldability and flexibility, the fluidity is improved by, for example, blending mineral oil or the like for the improvement. The technology is known.

[0004]

However, when a mineral oil or the like is blended with an acrylic resin or an MS resin, the transparency and weather resistance, which are the characteristics of these resins, are significantly impaired.
There is a problem that the effect of improving the fluidity is not sufficient.

[0005] The problem to be solved by the present invention is to improve the fluidity of acrylic resins, MS resins or their modified resins without deteriorating transparency or weather resistance. It is in.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in view of such a situation, and as a result, have found that acrylic resin (a1),
Alternatively, a specific aliphatic polyester (B) is added to a resin component (A) containing a copolymer resin (a2) obtained by polymerizing an acrylic monomer with an aromatic vinyl monomer in a proportion of 60% by weight or more. The present inventors have found that a thermoplastic resin composition characterized by the above as an essential component can solve the above-mentioned problems, and have completed the present invention.

That is, the present invention provides: (1) an acrylic resin (a1) or a copolymer resin (a2) obtained by polymerizing an acrylic monomer with an aromatic vinyl monomer in a proportion of 60% by weight or more. And a reaction product of an aliphatic dicarboxylic acid (b1) and a diol component (b2), and having a viscosity of 50 to 5,000 cps (25 ° C.) measured by a BM type viscometer. (2) The aliphatic dicarboxylic acid (b1) has 4 to 4 carbon atoms.
10 aliphatic dicarboxylic acids, and a diol component (b
(2) The composition according to the above (1), wherein the diol has 3 to 6 carbon atoms. (3) The aliphatic polyester (B) is 0.1 to 20% by weight based on the resin component (A). (4) The composition according to (1), (2) or (3), wherein the acrylic resin (a1) contains an acrylic rubber. (5) The copolymer resin (a2) comprises an acrylic monomer and an aromatic vinyl monomer in a weight ratio of the former / the latter (60 to 9).
(5) The composition according to (1), (2) or (3), which is copolymerized at a ratio of (40 to 5), (6) a copolymer resin (a2) is a rubbery polymer In the presence of, an aromatic vinyl monomer and an acrylic monomer,
The above (1), (2) or (3) wherein the acrylic monomer is graft-polymerized at a ratio of 60% by weight or more.
(7) The copolymer resin (a2) comprises an acrylic monomer and an aromatic vinyl monomer in the presence of a rubbery polymer in a weight ratio of the former to the latter (60 to 60). 95) / (40-5) the composition according to the above (6), which is obtained by graft polymerization at a ratio of: (8) the rubbery polymer constituting the copolymer resin (a2) is:
1 to 2 polybutadiene or aromatic vinyl monomer
The composition according to the above (6) or (7), which is a styrene-butadiene block copolymer rubber used at a ratio of 0% by weight, (9) the graft copolymer rubber particles in the copolymer resin (a2) are average particles. (6) having a diameter of 0.2 to 1.2 μm;
(7) The composition according to (8), (10) The above (1), (5), (6), (6), wherein methyl methacrylate and another acrylic monomer are used in combination as the acrylic monomer. 7) The composition according to (8) or (9),

(11) An acrylic monomer or a mixed solution of an acrylic monomer and a styrene monomer containing the acrylic monomer in a proportion of 60% by weight or more is mixed with at least one agitated solution. When producing the resin component (A) by polymerizing in a continuous bulk polymerization line incorporating a tubular reactor in which a tubular reactor in which a plurality of mixing elements having no moving parts and subsequently a plurality of mixing elements having no moving parts are fixed, (1) In the course of the polymerization line including the tubular reactor, the aliphatic dicarboxylic acid (b1) and the diol component (b2) are reactants, and have a viscosity of 50 to 5,000 cps (25 ° C. Or (2) dissolving the aliphatic polyester (B) in the acrylic monomer or mixed solution, while mixing the aliphatic polyester (B) which is Then the resin component The polymerization of A) is carried out, or (3) the resin component (A) obtained by removing the unreacted monomer or solvent by performing the polymerization is melt-kneaded with the aliphatic polyester (B). A method for producing a resin composition,

(12) An acrylic monomer or a mixed solution of an acrylic monomer and a styrene monomer containing the acrylic monomer in a proportion of 60% by weight or more is a. A reactor; b. An initial polymerization line consisting of one or more tubular reactors having a plurality of mixing elements fixed therein with no moving parts continuing from the stirred reactor; c. A continuous movement from the initial polymerization line A main polymerization line comprising one or more tubular reactors having a plurality of mixing elements having no parts fixed therein; d. Branching between the initial polymerization lines and A part of the initial polymerization liquid stream flowing out of the initial polymerization line is refluxed through the reflux line, while the initial polymerization liquid stream not refluxed is returned to the main polymerization line. When the resin component (A) is produced by polymerization with (a) an aliphatic dicarboxylic acid (b1) and a diol component (b2) in the course of a polymerization line including the tubular reactor, And the viscosity by a BM type viscometer is 50 to 5,000 cps (25 ° C.)
(2) polymerizing the graft copolymer (A) while mixing the aliphatic polyester (B), or (2) dissolving the aliphatic polyester (B) in the acrylic monomer or the mixed solution. Then, the resin component (A) is polymerized, or (3) the resin component (A) obtained by removing the unreacted monomer or solvent by performing the polymerization is melted with the aliphatic polyester (B). The production method according to the above (11), wherein the kneading is performed;

(13) A mixed solution of an acrylic monomer and a styrene monomer containing an acrylic monomer in a proportion of 60% by weight or more contains a rubbery polymer in addition to these components. The production method according to the above (11) or (12),

(14) A mixed solution of an acrylic monomer and a styrene monomer containing an acrylic monomer in a proportion of 60% by weight or more contains an acrylic monomer and an aromatic vinyl monomer. The body and the weight ratio of the former / the latter are (60-95) / (4
0 to 5), further comprising a rubbery polymer, the production method according to the above (13),

(15) The above (13) or (14), wherein the rubbery polymer is polybutadiene or a styrene-butadiene copolymer rubber used in a proportion of 1 to 20% by weight of an aromatic vinyl monomer. Manufacturing method. (16) The method according to any one of the above (11) to (15), wherein the aliphatic polyester (B) is contained at a ratio of 0.1 to 20% by weight based on the acrylic monomer or the mixed solution. A method for producing the same.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The acrylic resin (a) used in the present invention
As 1), an acrylic resin having an alkyl (meth) acrylate unit generally having an alkyl group having 1 to 4 carbon atoms as a main component is preferably exemplified. More specifically, it is preferably a copolymer of an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms and an alkyl acrylate having an alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl (meth) acrylate having an alkyl group include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Of these, methyl methacrylate is most preferred in terms of performance. .

Examples of the alkyl acrylate having an alkyl group having 1 to 4 carbon atoms to be copolymerized with the alkyl methacrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and the like. Of these, methyl acrylate and ethyl acrylate are preferred from the viewpoint of performance. The proportion of alkyl acrylate units contained in the acrylic resin is preferably 20% by weight or less,
More preferably, it is 0.5 to 10% by weight.

The acrylic resin (a1) preferably further contains an acrylic rubber from the viewpoint of impact resistance. Here, the acrylic resin containing acrylic rubber has a structure in which a rubbery polymer exhibiting rubber elasticity at room temperature is dispersed in a matrix resin containing methyl methacrylate as a main component.

The acrylic rubber is a publicly known and used acrylic ester polymer. Specific examples of the acrylic acid ester as a raw material monomer include ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Two or more monomers may be used in combination.

The copolymer resin (a2) used in the present invention is:
A copolymer of an acrylic monomer and an aromatic vinyl monomer, wherein the acrylic monomer is copolymerized at a ratio of 60% by weight or more based on the total of both.

That is, when the use ratio of the acrylic monomer is 60
When the amount is less than the weight percentage, excellent weather resistance is not exhibited.
Further, the use ratio of the acrylic monomer is preferably 95% by weight or less from the viewpoint of transparency and fluidity, that is, the acrylic monomer is excellent in balance between weather resistance, transparency and fluidity. / Aromatic vinyl monomer (weight ratio) is 60
/ 40 to 95/5, and among these properties, the acrylic monomer / aromatic vinyl monomer (weight ratio) is 60/4 from the viewpoint of improving transparency and fluidity.
A range from 0 to 80/20 is preferable.

The molecular weight of the copolymer resin (a2) is not particularly limited, but the weight average molecular weight (Mw) of the copolymer resin is 50,000 to 180,000 and the weight average molecular weight (Mw) is The ratio Mw / Mn of the number average molecular weight (Mn) is 1.
Those having a weight-average molecular weight (Mw) of from 80,000 to 150,000 are preferred.

The acrylic monomer constituting the copolymer resin (a2) is not particularly limited, but may have one carbon atom.
Preferred are alkyl (meth) acrylates having an alkyl group of from 8 to 8. Specific examples of the alkyl (meth) acrylate include methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Alkyl acrylate; methyl acrylate,
Examples include alkyl acrylates such as ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Among them, methyl methacrylate is most preferable from the viewpoint of performance. Further, in the copolymer resin (a2), it is preferable to use an alkyl methacrylate and an alkyl acrylate in combination. In this case, the alkyl acrylate is preferably 20% by weight or less, particularly 0.5 to 15% by weight. Is preferred.

Examples of the aromatic vinyl monomer constituting the copolymer resin (a2) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, isobutylstyrene,
Tertiary butyl styrene, o-bromostyrene, m
-Bromostyrene, p-bromostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene and the like. Among them, styrene and α-methylstyrene are preferred. When the copolymer resin (a2) contains α-methylstyrene at a ratio of 1 to 20% by weight, the heat resistance is remarkably excellent, which is preferable.

The copolymer resin (a2) in the present invention may be obtained by copolymerizing an acrylic monomer and an aromatic vinyl monomer as essential monomer components as described above.
It is preferable to graft copolymerize these monomers in the presence of the rubbery polymer because the impact resistance of the molded article can be remarkably improved.

The rubbery polymer used herein is not particularly limited, but includes, for example, polybutadiene,
Styrene-butadiene copolymer rubber, styrene-butadiene-styrene block copolymer rubber and its hydrogenated rubber, styrene-isoprene-styrene block copolymer rubber and its hydrogenated rubber, ethylene-propylene terpolymer rubber, butadiene-acrylonitrile copolymer Rubber, acrylic rubber, alkyl acrylate-butadiene copolymer rubber, and the like.

Among them, those having excellent impact strength, transparency and weather resistance of the final composition and suitable for the continuous bulk polymerization method include rubbery polymers such as polybutadiene and styrene-
Butadiene copolymer rubber, styrene-butadiene-styrene block copolymer rubber and its hydrogenated rubber, styrene-isoprene-styrene block copolymer rubber and its hydrogenated rubber, alkyl acrylate-butadiene copolymer rubber, and the like, alone. They can be used or two or more of them can be used in combination.

When a butadiene rubber polymer is used as the rubber polymer used in the present invention, for example,
It is a polybutadiene or styrene-butadiene copolymer rubber having a 5% by weight styrene solution viscosity of 5 to 40 centipoise, and the styrene skeleton content in the copolymer rubber is preferably 20% by weight or less as described above. Further, it is particularly preferable that the styrene skeleton content is 15% by weight or less.

The bonding mode between the styrene monomer and the butadiene monomer in the styrene-butadiene copolymer rubber includes a random bond, a block bond, and a tapered block bond. The effect of improving is remarkable, which is preferable. That is, as the bound styrene content of the copolymer rubber increases to 20% by weight, it is important to reduce the blocking ratio of the bound styrene in order to improve the weather resistance of the resin composition of the present invention. More specifically, a copolymer rubber having a styrene skeleton content of up to 10% by weight may have a large number of block bonds. The effect of improving the weather resistance is remarkably excellent.

Further, the polybutadiene and styrene-butadiene copolymer rubber used in the present invention has a 5% by weight styrene solution viscosity of 5 to 40 centipoise, which has a large effect of improving the impact resistance, and controls the rubber particle diameter during production. Is preferred in that it is easy, especially 5% by weight at 25 ° C.
Styrene solution viscosity is 9-30 centipoise and 10
Mooney viscosity of 20 to 8 using L rotor at 0 ° C
0 is preferred.

The above polybutadiene and styrene-butadiene copolymer rubber preferably has a 1,2-vinyl bond ratio of 7 to 35% of the unsaturated bonds based on the butadiene monomer, and more preferably a rubber having a 10 to 25% ratio. . In this case, the remainder of the 1,2-vinyl bond forms a cis and trans bond.

Here, the ratio of 1,2-vinyl bonds is 7%
When the above copolymer rubber is used, the content of toluene-insoluble components in the rubber-modified copolymer resin increases, and the impact resistance is improved. On the other hand, when the proportion of the 1,2-vinyl bond is 25% or less, the progress of crosslinking at a high temperature during production can be suppressed, while the grafting ratio can be increased, the rubber elasticity can be improved, and the impact resistance can be improved. The performance is improved. Further, when it falls within the range of 10 to 25%, the balance between the degree of grafting of the resin (A) and the degree of crosslinking is significantly improved, and the rubber elasticity is significantly improved.

Graft polymerization of an aromatic vinyl monomer and an acrylic monomer in the presence of the rubbery polymer described in detail at a ratio of 60% by weight or more of the acrylic monomer. The obtained copolymer resin (a2) preferably has a toluene-insoluble content at 25 ° C. of 10 to 25% by weight, and further satisfies the above-mentioned toluene-insoluble content, and has a swelling index due to toluene. 6 to 15, and the toluene insoluble content / swelling index is 0.80 to 2.50% by weight.
It is preferred that In this range, the rubber-modified copolymer resin has a good balance between the degree of grafting and the degree of cross-linking of the copolymer rubber in the resin, and balances the transparency, impact resistance and weather resistance of the molded article. Is remarkably good.

Further, the shape of the graft copolymer resin particles dispersed in the copolymer of the aromatic vinyl monomer and the acrylic monomer, which is the matrix resin, is not particularly limited, but will be described later. A copolymer resin (a) obtained by graft-polymerizing an aromatic vinyl monomer and an acrylic monomer in the presence of a rubbery polymer by a continuous bulk polymerization method described in detail.
In the case of 2), the so-called "salami structure" in which the matrix resin is occluded and dispersed in the graft copolymer rubber particles is preferable from the viewpoint of impact resistance. The average particle diameter of the graft copolymer resin particles is not particularly limited, but the average rubber particle diameter is 0.2.
It is preferably from 0 to 1.20 µm, and particularly preferably from 0.40 to 0.80 µm from the viewpoint of excellent transparency, impact resistance and weather resistance of the rubber-modified copolymer resin composition. In the present invention, even when the content of the toluene-insoluble matter at 25 ° C. is as high as 10 to 25% by weight, the average particle diameter can be reduced in this manner, and as a result, the transparency and the impact resistance are improved. And the effect is unprecedented.

Further, in the case where an aromatic vinyl monomer and an acrylic monomer are graft-polymerized in the presence of the rubbery polymer at a ratio of 60% by weight or more of the acrylic monomer. May further be graft-copolymerized with another copolymerizable monomer. Examples of the other copolymerizable monomer include vinyl-method such as (meth) acrylonitrile.
Cyan compounds; itaconic acid, maleic acid, fumaric acid,
Polymerizable unsaturated fatty acids such as crotonic acid and cinnamic acid; N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-octylmaleimide, N-isopropylmaleimide, N-phenylmaleimide, Np-bromophenylmaleimide And maleimides such as N-o-chlorophenylmaleimide and N-cyclohexylmaleimide;
Unsaturated carboxylic anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated compounds containing amino group such as allylamine, aminoethyl (meth) acrylate and aminopropyl (meth) acrylate And acrylamide compounds such as acrylamide and N-methylacrylamide.

On the other hand, the aliphatic polyester (B) used in the present invention comprises an aliphatic dicarboxylic acid (b1) and a diol (b).
A polyester obtained by reacting 2), and
Viscosity measured by a BM viscometer is 50 to 5,000 cps (2
5 ° C.) aliphatic polyester (B).

In the present invention, by using such an aliphatic polyester (B), the fluidity of the composition can be remarkably improved without impairing the transparency and weather resistance of the resin component (A). Further, the molding start temperature can be lowered as compared with the case where the resin component (A) is used alone. Therefore, the molding temperature range can be expanded, and the dependence of transparency on injection pressure during injection molding can be almost eliminated. By eliminating the injection pressure dependency of the transparency, it is possible to eliminate the transparency gradient between the gate portion and the terminal portion in, for example, a large injection molded product. Further, when this aliphatic polyester (B) is used, the oil resistance of the molded product can be remarkably improved.

Among the aliphatic polyesters (B), 10
The range of 0 to 2,000 cps is excellent in mixing dispersibility and compatibility when mixed with the resin component (A), and is also preferable from the viewpoint of transparency and surface appearance of a molded product. Further, its number average molecular weight is from 500 to 2,000, preferably from 700 to 2,000.
It is preferably 1500. Particularly, in the case of the resin component (A) containing a rubbery polymer, the aliphatic polyester (B) having a viscosity of 100 to 1000 cps (25 ° C.) by a BM type viscometer is extremely excellent in the transparency of a molded product,
In addition, it was found that there was no change in transparency due to the difference in molding conditions.

Specific examples thereof include a polyester of a linear aliphatic dicarboxylic acid and a diol and a polyester of an alicyclic dicarboxylic acid and a diol.
Polyesters of linear aliphatic dicarboxylic acids and diols are preferred.

These aliphatic polyesters (B) may be used alone or in combination of two or more.

Examples of the linear aliphatic dicarboxylic acid (b1) used herein include dibasic acids such as succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacine. Adipic acid is preferred because the effect of the above is remarkable.

The diol (b2) is not particularly limited, but ethylene glycol, 1,2
-Propanediol, 1,3-propanediol, 1,
3-butanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol and the like, among which the effect of the present invention is remarkable,
1,3-propanediol, 1,4-butanediol,
1,5-pentanediol is preferred.

As the combination of the aliphatic dicarboxylic acid and the diol, any of the above-mentioned compounds may be combined. Specifically, a polyester composed of adipic acid and 1,3-propanediol, When a polyester composed of adipic acid and 1,4-butanediol, and an aliphatic polyester composed of adipic acid and 1,5-pentanediol are mixed with the thermoplastic resin of the present invention, the viscosity range thereof is as follows. It is optimal and is preferable because the appearance of the molded article is excellent.

In the case where the polyester obtained by the reaction of the aliphatic dicarboxylic acid and the diol has a hydroxyl group at its molecular terminal, a monovalent organic acid such as acetic acid or a fatty acid is further used as a terminator as a terminator. When a carboxyl group is present at the molecular end, the reaction may be carried out using a monohydric alcohol as a terminator.

Here, the monovalent organic acid which can be used as a terminator includes, for example, those having 10 to 10 carbon atoms such as capric acid, lauric acid, myristic acid, stearic acid, palmitic acid, stearic acid, oleic acid and linoleic acid. 20 long-chain fatty acids or organic acids such as acetic acid. on the other hand,
Examples of the monohydric alcohol include methanol, ethanol, propanol, isopropanol, butanol,
Isobutanol, secondary butanol, tertiary butanol, n
-Amyl alcohol, n-hexanol, isohexanol, n-heptanol, n-octanol, 2-ethylhexanol, isooctanol, n-nonanol,
Examples include aliphatic alcohols such as isononanol, n-decanol, isodecanol, isoundecanol, lauryl alcohol, cetyl alcohol, and stearyl alcohol.

The amount of the monohydric organic acid or monohydric alcohol to be used as the terminator is not particularly limited, but is not more than 60% by weight based on the total amount of the monomer components including aliphatic dicarboxylic acid and diol. It is preferable to use them.

The specific method for producing the polyester is not particularly limited, and may be an aliphatic dicarboxylic acid,
A diol and a monohydric organic acid or a monohydric alcohol may be a so-called one-step method of reacting in the presence of a catalyst, or an aliphatic dicarboxylic acid and a diol may be reacted in the presence of a catalyst, A two-stage method in which a monovalent organic acid or a monohydric alcohol is reacted may be used.

As the catalyst, a conventionally known esterification catalyst,
For example, sulfuric acid, hydrochloric acid, toluene sulfonic acid, acid catalysts such as phosphoric acid, tetraisopropyl titanate, titanate catalysts such as tetrabutyl titanate, mono- or dimethyl tin oxide, mono- or dibutyl tin oxide, mono- or dioctyl tin oxide, mono- or dimethyl tin An organic tin catalyst such as chloride, mono- or dibutyltin chloride or the like can be used, but the use of an organic tin catalyst is preferred from the viewpoint of the transparency of the molded article.

The method for producing the resin composition of the present invention comprising the above-described resin component (A) and the aliphatic polyester (B) as essential components, that is, a method of mixing both is particularly limited. However, for example, the resin (a
Before polymerizing 1) or the copolymer resin (a2), the aliphatic polyester (B) is dissolved in the raw material monomer component of the resin (a1) or the copolymer resin (a2), and then the monomer component is dissolved. , A method of adding an aliphatic polyester (B) during the polymerization of the resin (a1) or the copolymer resin (a2), and a method of producing the resin (a1) or the copolymer resin (a2), A method of melt-kneading with the aliphatic polyester (B) is exemplified.

Regarding the above mixing method, for example, regardless of the polymerization method of the resin (a1) or the copolymer resin (a2), for example,
It can be applied to any polymerization method of bulk-suspension polymerization, solution polymerization and continuous bulk polymerization. In the case of bulk-suspension polymerization, a method of melt-kneading the aliphatic polyester (B) after polymerization is preferable. In the case of polymerization, a method of adding an alkyl ester (B) to a monomer component in advance is preferable. In addition, in the case of the continuous bulk polymerization method, a method of adding during the polymerization is preferable because productivity and workability are good.

Among these production methods, the resin (a
1) or a method for producing the copolymer resin (a2) by continuous bulk polymerization, in particular, producing a resin composition by the production method of the present invention described in detail below is extremely excellent in productivity,
Further, it is preferable because the uniformity of the composition becomes good and the effect of the present invention becomes remarkable.

That is, the production method of the present invention provides an acrylic monomer or a mixed solution of an acrylic monomer and a styrene monomer containing the acrylic monomer in a proportion of 60% by weight or more. Is polymerized in a continuous bulk polymerization line incorporating one or more agitated reactors and subsequently a tubular reactor in which a plurality of mixing elements without moving parts are fixed, to produce a resin component (A). (1) In the course of the polymerization line including the tubular reactor, the aliphatic dicarboxylic acid (b1) and the diol component (b2) are reactants and have a viscosity of 50 to 50 measured by a BM type viscometer. 5,000
Polymerizing the resin component (A) while mixing the aliphatic polyester (B) at cps (25 ° C.), or (2) adding the aliphatic polyester (B) in the acrylic monomer or the mixed solution. And then polymerizing the resin component (A), or (3) adding the aliphatic polyester (B) to the resin component (A) obtained by removing the unreacted monomer or solvent by performing the polymerization. ) And melt-kneading.

The continuous bulk polymerization line used in the production method of the present invention is a tubular reactor (hereinafter, referred to as “static”) in which one or more stirring reactors and a plurality of mixing elements having no moving parts are fixed. Abbreviated as "tubular reactor having a dynamic mixing element"), and using such a continuous bulk polymerization line, a continuous bulk polymerization is performed while performing static mixing using the tubular reactor. By performing the polymerization, the heat of polymerization generated in the polymerization of the acrylic monomer is efficiently removed, and even those having different viscosities can be easily mixed with each other, and the uniformity of the composition is significantly improved. Therefore, a resin composition having excellent transparency and weather resistance can be efficiently produced.

As such a method, specifically, for example, a polymerization method in which two stirred reactors are connected and then a continuous bulk polymerization line incorporating a tubular reactor having a static mixing element is connected. Using the line, the acrylic monomer or acrylic monomer
A mixed solution of an acrylic monomer and a styrene monomer contained in a proportion of 0% by weight or more (hereinafter, these acrylic monomers or the mixed solution is abbreviated as "raw material monomer") Is introduced into a stirred reactor, polymerization is carried out in a second stirred reactor to a polymerization rate of 40 to 60%, and then introduced into a continuous bulk polymerization line consisting of a tubular reactor having a static mixing element. The following continuous bulk polymerization method is preferable, since the function of a tubular reactor having a static mixing element can be maximized and productivity and operability are remarkably excellent.

That is, the starting monomers are graft-copolymerized in a continuous bulk polymerization line incorporating a stirred reactor followed by a tubular reactor in which a plurality of mixing elements without moving parts are fixed. At this time, (1) a method of performing the polymerization while mixing the aliphatic polyester (B) in the middle of a polymerization line including the tubular reactor (hereinafter, referred to as
This method is abbreviated as “method (1)”, (2) a method in which the aliphatic polyester (B) is dissolved in the raw material monomer, and then polymerization is performed (hereinafter, this method is referred to as “method (2) ))) Or (3) a resin (a1) or (a2) obtained by polymerizing to remove unreacted monomers or solvent.
And a method of melt-kneading with the aliphatic polyester (B) (hereinafter, this method is abbreviated as "method (3)"),
By mixing the aliphatic polyester (B) by the method (3), the obtained polymer composition can be controlled uniformly, and the alkyl esters (B) can be more uniformly dispersed, so that the transparency and weather resistance can be improved. It is preferable because a thermoplastic resin composition excellent in the above can be efficiently produced.

Among these, the method is particularly advantageous in that there is no melt-kneading step after the production of the resin, the productivity is excellent, and there is no change in hue due to the melt-kneading and the transparency becomes better. (1) and method (2) are preferred.

In the production method of the present invention, it is preferable to use a rubber component together with the raw material monomer and carry out graft copolymerization from the viewpoint of impact strength and weather resistance. Specifically, the resin (a1) In the above, an acrylic rubber can be used in combination with the acrylic monomer, and the copolymer resin (a2)
In the above, a rubbery polymer can be used for a mixed solution of an acrylic monomer and a styrene monomer containing the acrylic monomer in a proportion of 60% by weight or more.

As described above, when a rubber component is used in combination, the method (1) is preferable from the viewpoint that the uniform dispersion of the rubber particles in the composition is improved and the transparency is further improved.

Further, as a polymerization method using a continuous bulk polymerization line incorporating the above-mentioned stirring type reactor and a tubular reactor having a plurality of mixing elements having no moving parts fixed therein, the following are specific examples. The raw material monomer or a mixture of the raw material monomer and the rubber component is mixed with a. A stirred reactor, and b. An initial polymerization line consisting of one or more tubular reactors, and c. A main polymerization consisting of one or more tubular reactors having a plurality of mixing elements which are continuous with the initial polymerization line and have no moving parts. From the initial polymerization line using a polymerization line consisting of a line and a reflux line that branches between the initial polymerization line and the main polymerization line and returns to the initial polymerization line. A part of the initial polymerization liquid stream is refluxed through the reflux line, while the non-refluxed initial polymerization liquid stream is polymerized in the main polymerization line, thereby achieving uniform mixing of the polymerization liquid, efficient heat removal, and polymer composition. It is preferable from the viewpoint of uniformity.

When the resin (a1) or the copolymer resin (a2) is produced using the polymerization line constituted by the above a. To d., The above method ( In the case of 1), a method of adding the aliphatic polyester (B) from at least one of the points a. To d. In particular, from the viewpoint of production efficiency and the uniformity of rubber particles, it is preferable to add c in the main polymerization line.

When the aliphatic polyester (B) is added by the method (2), the aliphatic polyester (B) is previously dissolved in a raw material monomer or a mixture of a raw material monomer and a rubber component. After that, it is preferable to introduce into the stirred reactor a.

When mixing according to the method (3), the resin (a1) or the copolymer resin (a
After producing 2), a method of melt-kneading this with an aliphatic polyester (B) using an extruder or the like can be used.

Among them, as described above, the method is advantageous in that there is no melt-kneading step after the resin production, the productivity is excellent, and there is no change in hue due to the melt-kneading and the transparency is better. (1) and method (2) are preferred, in particular,
When a rubber component is used in combination, the method (1) is preferred from the viewpoint that the uniform dispersibility of the rubber particles in the composition is improved and the transparency is further improved.

An example of the continuous bulk polymerization method will be described below with reference to the drawings. FIG. 1 is a process diagram showing an example of a continuous bulk polymerization line incorporating a tubular reactor having a static mixing element.

The raw material monomer or the mixture of the raw material monomer and the rubber component supplied by the plunger pump (1) is first sent to a stirred reactor (2), and after initial polymerization under stirring, By means of a gear pump (3), it is fed to a circulating polymerization line (I) having a tubular reactor (4), (5) and (6) with static mixing elements and a gear pump (7).

When a rubber component is used in combination, the initial polymerization in the stirred reactor (2) and the circulation polymerization line (I) are combined with each other, so that the rubber particles are not subjected to excessive shearing and the efficiency of the rubber particles is improved. This is preferable in that a finer composition can be achieved, and the polymer composition in the polymerization step can be made uniform.

In the initial polymerization in the stirred reactor (2), the polymerization conversion of the raw material monomer is 10 to 32% by weight, preferably 14 to 28% by weight at the outlet of the reactor (2). It is implemented to be. The stirring reactor (2) includes, for example, a stirring tank reactor, a stirring tower reactor, and the like, and the stirring blade includes, for example, an anchor type, a turbine type, a screw type, a double helical type, and the like. Stirring blades.

In the present invention, a solvent may be used to reduce the viscosity of the mixed solution in the reactor, and the amount of the solvent used is 5 to 20 parts by weight based on 100 parts by weight of the total amount of the raw material monomers. . As the type of the solvent, toluene, ethylbenzene, xylene and the like which are usually used in the bulk polymerization method are suitable.

In the present invention, it is preferable to add a chain transfer agent to the raw material monomer liquid for controlling the molecular weight of the resin (a1) or the copolymer resin (a2). The amount of the chain transfer agent to be added is generally in the range of 0.05 to 0.5 part by weight based on 100 parts by weight of the total amount of the raw material monomers. The mixed solution initially polymerized under dynamic stirring as described above is then polymerized while circulating in the circulation polymerization line (I),
Part of it is sent continuously to a non-circulating polymerization line (II) in which tubular reactors (8), (9) and (10) with static mixing elements are incorporated in series.

When the rubber component is used together with the raw material monomer, the rubber particles in the raw material monomer in the circulation polymerization line (I) are statically circulated in the circulation polymerization line (I). And the particle size is stabilized, and the particle size is also fixed. In this case, the important factors are the reflux ratio (R) of the mixed solution in the circulation polymerization line (I) and the polymerization conversion rate of the raw material single particles.

The reflux ratio (R) is determined in the non-circulating polymerization line (II).
The flow rate of the polymerization solution which is refluxed in the circulation polymerization line (I) without flowing out to the circulation polymerization line (I) is defined as F1 (liter / hour), and the flow rate F2 of the polymerization solution flowing out of the circulation polymerization line (I) to the non-circulation polymerization line (II). (Liter / hour), usually R = F
1 / F2 is in the range of 3 to 15, and the pressure loss in the tubular reactor is reduced. In addition, when a rubber component is used, the generated rubbery polymer particles are stable and have a small particle size. In particular, the range of R = 5 to 10 is particularly preferable in that it can be performed.

In the graft polymerization in the circulating polymerization line (I), the polymerization conversion of the raw material monomer at the outlet of the circulating polymerization line (I) is generally 35 to 65% by weight, preferably 4 to 65% by weight.
The polymerization is carried out so as to be 0 to 60% by weight. A suitable polymerization temperature is 120 to 135 ° C.

The polymerization liquid polymerized in the circulation polymerization line (I) is then supplied to the non-circulation polymerization line (II),
At a polymerization temperature of 40 to 160 ° C, the conversion of the starting monomer is 60
It is continuously polymerized until it reaches ８５85% by weight. Next, this mixed solution is sent to a preheater and then to a devolatilization tank by a Kia pump (11), and after removing unreacted monomers and a solvent under reduced pressure, pelletizing the resin (a1). ) Or a copolymer resin (a2) is obtained. At this time, it is preferable to perform the preheating and the devolatilization under the condition that the increase in the conversion rate in the preheater and the devolatilization tank is 7% by weight or less.

As the plurality of mixing elements fixed inside the tubular reactor having the static mixing element used in the present invention, for example, the flow of the polymerization liquid flowing into the pipe is changed and the flow direction is changed, Is repeated to mix the polymerization liquid. As such a tubular reactor, for example, SMX type, SMR
Sulzer-type tubular mixers, Kenix-type static mixers, and Toray-type tubular mixers are preferred.

The number of these tubular reactors to be incorporated in the circulation polymerization line (I) or the non-circulation polymerization line (II) is particularly different in the case of the above-mentioned tubular reactor because it depends on the length, the structure of the mixing element and the like. Without limitation, the tubular reactor having four or more mixing elements
１５15, preferably 6-10 are used in combination. Among them, the number of the tubular reactors to be incorporated in the circulation polymerization line (I) is usually 1 to 10, preferably 2 to 6.

The raw material monomer or the mixture of the raw material monomer and the rubber component in the production method of the present invention may optionally contain an organic peroxide which releases a free radical when decomposed as a polymerization initiator. This is preferable because kraft formation and promotion of the reaction can be performed at a relatively low temperature. The addition amount is 0.005 to 0.5 parts per 100 parts by weight of the raw material monomer.
It is in the range of 04 parts by weight.

The organic peroxide used here is preferably one having a half-life of 10 hours at a temperature of 75 to 170 ° C., and specific examples thereof include 1,1-di-t-butylperoxycyclohexane, , 1-Di-t-butylperoxy-
3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxy-2-methylcyclohexane, 2,2-bis (4,
4-di {-tert-butylperoxycyclohexyl) propane, 2,2-di-tert-butylperoxyoctane, n-butyl-4,4-di-tert-butylperoxyvalerate, 2,2-di -Peroxy ketals such as t-butyl peroxybutane; t-butyl peroxy acetate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy Oxybenzoate, t-butyl peroxymetharate, di-t-butyl diperoxyisophthalate, 2,5-dimethyl-2,5-
Dibenzoyl peroxyhexane, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide,
Peroxyesters such as cumene hydroperoxide and the like can be mentioned, and these are used alone or in combination of two or more.

The raw material monomer or the mixture of the raw material monomer and the rubber component used in the present invention may contain, if necessary, a plasticizer such as a mineral oil, an antioxidant, a chain transfer agent, and a long-chain fatty acid. A release agent such as an ester or a metal salt thereof, and a publicly-used additive such as silicone oil may be used in combination.

The resin composition thus obtained can further contain commonly used antioxidants, plasticizers, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, foaming agents, reinforcing materials and the like. .

As specific examples, for example, mineral oil,
Examples include ester plasticizers, organic polysiloxanes, higher fatty acids and metal salts thereof, hindered phenolic antioxidants, glass fibers, and the like, each of which can be used alone or in combination. In particular, specific examples of additives generally used for improving weather resistance include Tinuvin P and Tinuvin 3
Benzotriazole-based or benzophenone-based ultraviolet absorbers represented by No. 27 (Nippon Ciba-Geigy Co., Ltd.), Irganox 1076 (Nippon Ciba-Geigy Co., Ltd.), Sumilizer GM, GS (Sumitomo Chemical Co., Ltd.)
Hindered phenolic antioxidant represented by, hindered amine light stabilizer represented by SANOL LS-770, phosphorus-based antioxidant represented by trisnonylphenyl phosphite, dimyristyl thiodipropionate Representative examples include organic sulfur-based antioxidants. Like the aliphatic polyester of the present invention, the additive used for improving weather resistance may be added during resin production, or may be melt-mixed using an extruder or the like after producing the resin of the present invention. good.

The use of the resin composition of the present invention described in detail above is not particularly limited.
Alternatively, it is useful in profile extrusion molding of an IC carrier magazine rail or the like.

The method for producing the sheet is not particularly limited, and the resin composition of the present invention is melt-extruded, continuously extruded from a T-die, a circular die, or the like, and cooled or adjusted to a temperature suitable for stretching. Stretching ratio, for example, 1 to 2 to 5 times
A method of stretching to an area stretching ratio in a biaxial or biaxial manner may, for example, be mentioned. Alternatively, the melt-extruded raw material may be cooled once and then stretched by reheating again to an area ratio of 3 to 15 times.
The thickness of the sheet is not particularly limited, and usually,
Although the thickness is 0.01 to 10.0 mm, a preferable range in which the strength improving effect is remarkably exhibited is as follows:
It is preferably 5.0 mm.

Further, the resin composition of the present invention can be prepared by injection molding,
Various molded articles can be used by molding methods such as single-screw extrusion molding, biaxial stretching extrusion molding, inflation extrusion molding, profile extrusion molding, vacuum molding, pressure molding, and blow molding. Its applications are wide-ranging, such as lighting, signboards, displays, electrical components, weak electrical components, building materials such as carport sunroofs, blister packs, shrink films, and the like. It can be used as various parts of OA equipment such as a copying machine, a printer, a facsimile, a personal computer, etc., and a part of medical instruments.

The rubber-modified copolymer resin composition of the present invention may further comprise a polystyrene resin, a rubber-modified polystyrene resin, an AS resin, an ABS resin, a styrene-methyl methacrylate copolymer resin, a rubber-modified styrene-methacrylic acid, if necessary. A thermoplastic resin such as a methyl copolymer resin, a (meth) acrylic resin, a styrene-maleic anhydride copolymer resin, a styrene- (meth) acrylic acid copolymer resin, a polycarbonate resin, and a vinyl chloride resin is appropriately added. You can also.

[0083]

The present invention will be described more specifically below with reference to examples and comparative examples. However, all parts in the examples are parts by weight, and all percentages are percentages by weight except for the total light transmittance.

The methods for evaluating the total light transmittance, haze, weather resistance and fluidity are described below.

1. Average particle size of graft copolymer resin particles in resin Take transmission electron micrograph by ultra-thin section method of resin,
The particle diameter of 1000 particles in the photograph was measured, and the average particle diameter was determined by the following equation.

[0086]

(Equation 1) (However, ni is the number of rubber particles having a particle diameter Di.) The rubber particle distribution was also observed using a laser type particle size distribution analyzer LA-910 (manufactured by HORIBA, Ltd.).

2. Total light transmittance and haze A test piece having a thickness of 2 mm was prepared by an injection molding method, and the value was determined in accordance with ASTM D-1003.

3. For those containing rubbery polymers, the specimens for impact strength were measured for their impact strength in accordance with “JIS K-6871”, and then a weather meter (WEL made by Suga Test Instruments)
-SUN-DCH-B) was exposed to an isopod impact strength test
After a lapse of 0 hours, the test piece was taken out and the impact strength was measured, and the retention was calculated as follows. For resin compositions containing no rubbery polymer, see JIS K-711
3) before and 50 after weather meter exposure
After 0 hour, the yield strength was measured, and the retention was calculated as follows.

[0089]

(Equation 2)

4. Fluidity test The melt flow rate was measured according to “ASPM B-1238 (230 ° C., 3.8 kg)”.

The improvement rate of the melt flow rate was calculated as follows.

[0092]

(Equation 3)

Reference Example 1 A mixed solution composed of 25 parts of styrene, 70 parts of methyl methacrylate, 5 parts of butyl acrylate, and 10 parts of ethylbenzene was prepared.
Parts per part 0.2 parts n-dodecyl mercaptan and 0.2 parts per 100 parts of monomer mixture as organic peroxide.
015 parts of 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane were added and continuous bulk polymerization was carried out using an apparatus arranged as shown in FIG.

That is, the mixed solution containing each of the above components was sent to a 20-liter stirred reactor (2) by a plunger pump (1), and subjected to initial graft polymerization under dynamic mixing by a stirring blade. Was sent to the initial polymerization line (I) by the gear pump (3) to perform polymerization. still,
The initial polymerization line (I) is a tubular reactor having an inner diameter of 2.5 inches (30 SMX static mixers and 30 static mixing elements manufactured by Gebrüder Sulzer, Switzerland) in order from the inlet (4), (5) and (6) And a gear pump (7) for circulating the mixed solution. An outlet is provided between the tubular reactor (6) and the reflux line (V) having the gear pump (7), following the main polymerization line (V). In the main polymerization line (V), tubular reactors (8), (9) and (10) similar to the above are sequentially provided from the inlet.
And a gear pump (11) are connected in series.

The conditions for this polymerization are as follows. Continuous supply amount of mixed solution: 10 liters / hour Reflux ratio R: 7 Reaction temperature in stirred reactor (2): 115 ° C Reaction temperature in initial polymerization line (III): 130 ° C Main polymerization line (IV) Reaction temperature in 140) to 160 ° C. The mixed solution obtained by polymerization in this manner is heated to 235 ° C. by a heat exchanger, volatile components are removed under a reduced pressure of 50 mmHg, and the mixture is pelletized. A polymer resin was obtained. This is called resin A1. Then the haze value of this was measured,
The result was used as the reference value of the “degree of decrease in transparency” in Example 1. Further, the melt flow rate of this product was measured and used as a reference value of the improvement rate of the melt flow rate.

Reference Example 2 Styrene-butadiene random copolymer rubber [5% SV:
25 centipoise, styrene / butadiene weight ratio: 10/9
0] 8 parts, styrene 30 parts, methyl methacrylate 65
Parts of butyl acrylate and 10 parts of ethylbenzene were used in the same manner as in Reference Example 1 to obtain a rubber-modified copolymer resin of the present invention. This is called resin A2. Next, the haze value of this product was measured, and the result was used as the reference value of the “degree of decrease in transparency” in Example 3. Further, the melt flow rate of this product was measured and used as a reference value of the improvement rate of the melt flow rate.

Example 1 25 parts of styrene, 70 parts of methyl methacrylate, 5 parts of butyl acrylate, and 3 parts of aliphatic polyester (B) (viscosity 200 cps) composed of adipic acid and butanedil whose molecular terminals were sealed with octyl alcohol , And 10 parts of ethylbenzene, and 0.2 part of n-dodecylmercaptan as a chain transfer agent and 100 parts of the monomer mixture as an organic peroxide were added to 100 parts of the monomer mixture. 0.015 parts of 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane was added, and continuous mass was formed using an apparatus arranged as shown in FIG. Polymerization was performed.

The mixed solution obtained by the polymerization was heated to 235 ° C. in a heat exchanger, and volatile components were removed under a reduced pressure of 50 mmHg, followed by pelletization to obtain a copolymer resin composition of the present invention. Table 1 shows the measurement results of the physical properties of the resin.

Example 2 97 parts of a rubber-modified polymethyl methacrylate resin (Sumitomo Chemical Co., Ltd .; SUMIPEX HT55X), an aliphatic polyester (B) composed of adipic acid and butanedil having a molecular end sealed with octyl alcohol (viscosity) 1000
cps) After mixing 3 parts, cylinder temperature 200 °
The mixture was melt-kneaded with a twin-screw extruder having a diameter of 50 mm to obtain pellets of the target thermoplastic resin composition. Table 1 shows the measurement results of the physical properties of the resin. In addition, the above "SUMIPEX HT55
The haze value of "X" was measured, and the result was used as the reference value of "degree of decrease in transparency" in this example.

Example 3 Styrene-butadiene random copolymer rubber [5% SV:
25 centipoise, styrene / butadiene weight ratio: 10/9
0] 8 parts, styrene 30 parts, methyl methacrylate 65
Part, butyl acrylate and 5 parts of ethylbenzene using a mixed solution, and 3 parts of aliphatic polyester (B) (viscosity: 200 cps) composed of adipic acid and butanedil whose molecular terminals are sealed with octyl alcohol. A rubber-modified copolymer resin composition of the present invention was obtained in the same manner as in Example 1 except that it was added before the reactor (8). Table 1 shows the measurement results of the physical properties. Incidentally, the average particle diameter of the graft copolymer resin in the obtained composition was 0.60 μm, and the rubber particle distribution was uniform.

Comparative Example 1 Except that 3 parts by weight of liquid paraffin (S-250, manufactured by Witco Chemical) was used in place of the aliphatic polyester (B) comprising adipic acid and butanedil whose molecular terminals were sealed with octyl alcohol. In the same manner as in Example 3, a rubber-modified copolymer resin composition was obtained. Table 1 shows the measurement results of the physical properties.

[0102]

[Table 1]

The criteria in Table 1 are as follows. Degree of decrease in transparency (%): Difference in haze value of molded product with and without aliphatic polyester (mineral oil)

[0104]

According to the present invention, the flowability of a resin such as an acrylic resin, an MS resin, or a rubber-modified resin thereof can be improved without deteriorating the transparency and weather resistance. .

Further, in the present invention, not only these effects, but also the oil resistance of the molded product is remarkably excellent. Further, when continuous bulk polymerization is performed, the productivity is remarkably improved. Therefore, the thermoplastic resin composition obtained by the production method of the present invention is excellent in practical strength of transparency, weather resistance or impact resistance, and excellent in fluidity, so that it can be suitably used for various molded articles.

[Brief description of the drawings]

FIG. 1 is a process diagram showing an example of a continuous polymerization line incorporating a tubular reactor having a static mixing element therein.

[Explanation of symbols]

(1): Plunger pump (2): Stirred reactor (3): Gear pump (4): Tubular reactor having a static mixing element inside (5): Tubular reactor having a static mixing element inside (6): Tubular reactor having a static mixing element inside (7): Gear pump (8): Tubular reactor having a static mixing element inside (9): Tubular reactor having a static mixing element inside (10): Tubular reactor having a static mixing element inside (11): Gear pump (I): Initial polymerization line (II): Main polymerization line

Claims (16)

[Claims] 1. A resin component (A) containing an acrylic resin (a1) or a copolymer resin (a2) obtained by polymerizing an acrylic monomer with an aromatic vinyl monomer in a proportion of 60% by weight or more. And a reaction product of the aliphatic dicarboxylic acid (b1) and the diol component (b2), and having a viscosity of 5 by a BM type viscometer.
A resin composition comprising, as an essential component, an aliphatic polyester (B) of 0 to 5,000 cps (25 ° C.). 2. The composition according to claim 1, wherein the aliphatic dicarboxylic acid (b1) is an aliphatic dicarboxylic acid having 4 to 10 carbon atoms, and the diol component (b2) is a diol having 3 to 6 carbon atoms. Stuff. 3. The composition according to claim 1, wherein the aliphatic polyester (B) is contained in an amount of 0.1 to 20% by weight based on the resin component (A). 4. The composition according to claim 1, wherein the acrylic resin (a1) contains an acrylic rubber. 5. The copolymer resin (a2) contains an acrylic monomer and an aromatic vinyl monomer in a ratio of (60 to 95) / (40 to 5) by weight ratio of the former / the latter. 4. The composition according to claim 1, which is copolymerized. 6. A copolymer resin (a2) comprising an aromatic vinyl monomer and an acrylic monomer in the presence of a rubbery polymer, wherein the acrylic monomer is not less than 60% by weight. 4. The composition according to claim 1, wherein the composition is graft-polymerized at a certain ratio. 7. A copolymer resin (a2) comprising an acrylic monomer and an aromatic vinyl monomer in the presence of a rubbery polymer in the former / latter weight ratio of (60-95) / (40-5)
7. The composition according to claim 6, wherein the composition is obtained by graft polymerization at the following ratio. 8. The rubbery polymer constituting the copolymer resin (a2) is polybutadiene or a styrene-butadiene copolymer rubber using an aromatic vinyl monomer at a ratio of 1 to 20% by weight. A composition according to claim 6 or claim 7. 9. The composition according to claim 6, wherein the graft copolymer rubber particles in the copolymer resin (a2) have an average particle size of 0.2 to 1.2 μm. 10. The composition according to claim 1, wherein methyl methacrylate and another acrylic monomer are used in combination as the acrylic monomer. 11. An acrylic monomer or a mixed solution of an acrylic monomer and a styrene monomer containing the acrylic monomer in a proportion of 60% by weight or more by one or more stirring methods. When producing a resin component (A) by polymerizing in a continuous bulk polymerization line incorporating a tubular reactor in which a tubular reactor in which a plurality of mixing elements having no moving parts and subsequently a moving part are fixed is incorporated, (1) ) In the course of the polymerization line including the tubular reactor, a reaction product of the aliphatic dicarboxylic acid (b1) and the diol component (b2), and having a viscosity of 50 to 5, as measured by a BM viscometer.
Polymerization of the resin component (A) while mixing the aliphatic polyester (B) at 2,000 cps (25 ° C.), or (2) the aliphatic polyester (B) in the acrylic monomer or the mixed solution. And then polymerizing the resin component (A), or (3) adding the aliphatic polyester (B) to the resin component (A) obtained by removing the unreacted monomer and solvent by performing the polymerization. ) And melt-kneading the resin composition. 12. An acrylic monomer or a mixed solution of an acrylic monomer and a styrene monomer containing the acrylic monomer in a proportion of 60% by weight or more, a. A. An initial polymerization line consisting of one or more tubular reactors having a plurality of mixing elements fixed therein with no moving parts continuing from the stirred reactor; c. A moving part continuing from the initial polymerization line A main polymerization line consisting of one or more tubular reactors, in which a plurality of mixing elements without any of the above are fixed, d. A part of the initial polymerization liquid stream exiting from the initial polymerization line is refluxed through the reflux line using a polymerization line constituted by a return reflux line, and the initial polymerization liquid stream that has not been refluxed is overlapped in the main polymerization line. When the resin component (A) is produced by combining: (1) an aliphatic dicarboxylic acid (b1) and a diol component (b2) are reactants in the course of a polymerization line including the tubular reactor, and , The viscosity of the BM type viscometer is 50 to 5,
The graft copolymer (A) is polymerized while mixing the aliphatic polyester (B) at 2,000 cps (25 ° C.), or (2) the aliphatic polyester (B) is mixed in the acrylic monomer or the mixed solution. B) is dissolved and then the resin component (A) is polymerized, or (3) the aliphatic polyester is added to the resin component (A) obtained by removing the unreacted monomer and solvent by performing the polymerization. The production method according to claim 11, wherein the mixture is melt-kneaded with (B). 13. A mixed solution of an acrylic monomer and a styrene monomer containing an acrylic monomer in a proportion of 60% by weight or more contains a rubbery polymer in addition to these components. The production method according to claim 11 or 12, wherein 14. A mixed solution of an acrylic monomer and a styrene monomer containing an acrylic monomer in a proportion of 60% by weight or more, comprising an acrylic monomer and an aromatic vinyl monomer With the former / latter weight ratio of (60-95) / (40-
14. The production method according to claim 13, wherein the content is 5) and the rubbery polymer is further contained. 15. The method according to claim 13, wherein the rubbery polymer is polybutadiene or a styrene-butadiene copolymer rubber used in a proportion of 1 to 20% by weight of an aromatic vinyl monomer. 16. The method according to claim 11, wherein the aliphatic polyester (B) is contained in a proportion of 0.1 to 20% by weight based on the acrylic monomer or the mixed solution. Production method.