JPH107869A - Resin composition for sizing and sizing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having excellent heat resistance, weatherability and extrudability, and useful as a sizing material fitting on an outer wall of a house by containing a specific ratio of a polycarbonate resin and a polymethyl methacrylate resin. SOLUTION: This resin composition is composed of (A) 90-10 pts.wt. of a polycarbonate resin [e.g. the one obtained by a transesterification of a compound of the formula R is H, a halogen or a 1-8C alkyl; X is a single bond, a 1-8C alkylene, S, 0, etc.; (n) and (n') are each 0-4} with a diester carbonatel and (B) 10-90 pts.wt. of a polymethyl methacrylate resin, and preferably further contains (C) an impact resistance improving material such as an ABS resin, an AES resin, an AAS resin, an ACS resin, an MBS resin or acrylic rubber in an amount of 1-50 pts.wt. based on 100 pts.wt. of components (A+B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for producing a siding material to be attached to an outer wall of a house, and a siding material using the resin composition as a raw material. The present invention relates to a siding resin composition and a siding material that simultaneously achieve heat resistance, heat resistance, and excellent weathering resistance.

[0002]

2. Description of the Related Art At present, the exterior walls of houses (hereinafter referred to as sidings) are generally made of painted metal, ceramics, etc., but in the future, they can be reduced in weight and made unpainted, and furthermore, rustproof and processed. It is expected to be replaced by engineering plastics with excellent properties. Among them, vinyl chloride resin (hereinafter PVC) has excellent extrusion processability,
It is expected to expand to this application. However, P
VC is inferior to the conventional metal siding in terms of weather resistance, heat resistance, and impact resistance, and is in a direction opposite to the current world in terms of environmental aspects such as dehalogenation. Therefore, the emergence of engineering plastics that solves these problems is expected.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a resin composition suitable for producing a siding material made of engineering plastics having improved impact resistance, heat resistance and weather resistance. It is an object to provide a siding material using such a composition.

[0004]

The present inventors have made intensive studies to solve this problem, and as a result, have found that a resin composition comprising a polycarbonate resin and a polymethyl methacrylate resin, and a resin containing an impact resistance modifier as required. The inventors have found that the above-mentioned problems can be solved by processing and producing the composition using an extruder, and have completed the present invention.

That is, the present invention relates to a siding resin composition comprising (A) 90 to 10 parts by weight of a polycarbonate resin and (B) 10 to 90 parts by weight of a polymethyl methacrylate resin, and the components (A) and (B) The present invention relates to a siding resin composition containing 1 to 50 parts by weight of an impact resistance modifier (C) based on 100 parts by weight in total, and a siding material processed and manufactured by an extrusion molding means.

[0006] The polycarbonate resin (component A) is an aromatic homopolycarbonate or copolycarbonate produced by reacting a dihydric phenol with a carbonate precursor. Further, the polycarbonate of the present invention may be branched. Such branched polycarbonates are obtained as branched thermoplastic branched polycarbonates by reacting a polyfunctional aromatic compound with a dihydric phenol and a carbonate precursor.

The method for producing the polycarbonate of the present invention is known per se, and is a method for synthesizing a polycarbonate by transesterification of a dihydric phenol and a carbonic acid diester in a molten state, or reacting a dihydric phenol with phosgene in a solution. Methods (especially the interface method) are known.

For example, JP-A-2-175723, JP-A-2-12493
4, U.S. Pat.Nos. 4,001,184, 4,238,569, 4,238,5
No. 97, 4,474,999.

The aromatic dihydroxy compound is not particularly limited, and various known compounds can be used. For example, it is a compound having a phenolic hydroxyl group having a structure represented by the general formula (Formula 1).

[0010]

Embedded image

(Wherein R is a hydrogen atom, a halogen atom (eg, chlorine, bromine, fluorine, iodine) or a carbon atom having 1 to 8 carbon atoms)
When R is plural, they may be the same or different, and n and n ′ are 0
~ 4. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms,
To 15 cycloalkylene groups, cycloalkylidene groups having 5 to 15 carbon atoms, or -S-, -SO-, -SO2-, -C
It represents an O-, -O- bond or a bond represented by the general formula (Formula 2). )

[0012]

Embedded image

Examples of such a dihydric phenol include bis (4hydroxyphenyl) methane, 1,1bis (4hydroxyphenyl) ethane, 1,2bis (4hydroxyphenyl) ethane, and bis (4hydroxyphenyl) Phenylmethane, bis (4hydroxyphenyl) diphenylmethane, 2,2bis (4hydroxyphenyl)
Propane, 2,2 bis (4 hydroxyphenyl) butane, 1,1 bis (4 hydroxyphenyl) cyclohexane, bis (3,5 dimethyl-4-hydroxyphenyl) methane, 1,1 bis (3,5 dimethyl-4 hydroxyphenyl) ) Ethane, 1,2 bis (3.5 dimethyl-4-hydroxyphenyl) ethane, 2,2 bis (3.5 dimethyl-4-hydroxyphenyl) propane, 2,2 bis (3.5 dimethyl)
-4-hydroxyphenyl) butane, bis (3.5 dimethyl)
-4-hydroxyphenyl) phenylmethane, bis (3.5)
Dimethyl-4-hydroxyphenyl) diphenylmethane,
Bis (3,5 dichloro-4-hydroxyphenyl) methane,
2,2bis (3,5dichloro-4-hydroxyphenyl) propane, bis (3,5dibromo-4-hydroxyphenyl)
Dihydroxyarylalkanes such as methane, 2,2bis (3,5 dibromo-4hydroxyphenyl) propane, bis (4hydroxyphenyl) sulfone, bis (3,5dimethyl-4-hydroxyphenyl) sulfone, bis (3.5) Dihydroxyarylsulfones such as dibromo-4hydroxyphenyl) sulfone; dihydroxy such as bis (4hydroxyphenyl) ether, bis (3,5dimethyl-4hydroxyphenyl) ether and bis (3,5dibromo-4hydroxyphenyl) ether Aryl ethers, bis (4hydroxyphenyl) sulfide, bis (3,5dimethyl-4hydroxyphenyl) sulfide, bis (3,5dibromo-4hydroxyphenyl)
Dihydroxyaryl sulfides such as sulfides,
Examples thereof include dihydroxyaryl ketones such as 4,4 ′ dihydroxybenzophenone, sulfoxides such as bis (4hydroxyphenyl) sulfoxide, and bis (4hydroxyphenyl) thioether.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. In addition to the above, as the aromatic dihydroxy compound, the following general formula (Formula 3):

[0015]

Embedded image

(Where R ^f is each independently a carbon number of 1 to
It is 10 hydrocarbon groups or a halogen compound or a halogen atom, and m is an integer of 0 to 4. For example, resorcinol, and 3-methylresorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol, 3-tert-butylresorcinol,
3-phenylresorcinol, 3-cumylresorcinol, 2,3,
Substituted resorcinols such as 4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin; catechol; hydroquinone, and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3 -T-butylhydroquinone, 3
-Phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,
5,6-tetra-t-butylhydroquinone, 2,3,5,6
A substituted hydroquinone such as -tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, and the following formula (Formula 4)

[0017]

Embedded image

2,2,2 ', 2'-tetrahydro-3,
3,3 ′, 3′-Tetramethyl-1,1′-spirobis (1H-indene) -7,7 ′ diol can also be used.

These aromatic dihydroxy compounds may be used alone or in combination of two or more.

There are no particular restrictions on the carbonic acid diester. For example, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl Examples include, but are not limited to, carbonate, dicyclohexyl carbonate, and the like. Preferably, diphenyl carbonate is used.

These carbonates may be used alone or in combination of two or more.

In addition, a dicarboxylic acid or a dicarboxylic acid ester may be contained as an acid component. Examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; fats such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decandioic acid, dodecanedioic acid Aromatic dicarboxylic acids; cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid,
Alicyclic dicarboxylic acids such as 1,2'-cyclopentanedicarboxylic acid, 1,3-cyclopentanecarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid Can be mentioned.

Examples of the dicarboxylic acid ester include dimethyl, diethyl, diphenyl, methylphenyl and ditoluyl esters of the above-mentioned dicarboxylic acids.

These dicarboxylic acids or dicarboxylic acid esters may be used alone or in combination of two or more.

The dicarboxylic acid or dicarboxylic acid ester is contained in the above-mentioned diester carbonate in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.

In producing the polycarbonate, a polyfunctional compound having three or more functional groups in one molecule can be used together with the aromatic dihydroxy compound and the carbonic acid diester. As these polyfunctional compounds, compounds having a phenolic hydroxyl group or a carboxyl group are preferable, and compounds having three phenolic hydroxyl groups are particularly preferable.

Preferred specific examples of such compounds include 1,1,1-tris (4-hydroxyphenyl) ethane,
2,2 ', 2 "-tris (4-hydroxyphenyl) diisopropylbenzene, α-methyl-α, α', α'-tris (4-
Hydroxyphenyl) -1,4-diethylbenzene, α,
α ', α "tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane-2, 1,3,5-tri (4-hydroxyphenyl) benzene, 2,2-bis- (4,4- (4,4′-dihydroxyphenyl) -cyclohexyl) -propane, trimetic acid,
Examples include 3,5-benzenetricarboxylic acid and pyromellitic acid.

More preferably, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-
(Hydroxyphenyl) -1,3,5-triisopropylbenzene or the like.

The polyfunctional compound is preferably 0.03 mol or less, more preferably 0.001 to 0.02 mol, particularly preferably 0.01 to 0.02 mol, per mol of the aromatic dihydroxy compound. It can be molar.

Polymethyl methacrylate resin (component B)
Is a thermoplastic resin composition containing methyl methacrylate as a main component. However, it may further contain an alkyl ester of methacrylic acid exemplified by ethyl methacrylate, propyl methacrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, and the like. Further, other copolymerizable components may be contained as long as the basic characteristics of PMMA are not impaired.

The mixing ratio of the above components (A) and (B) is 10 to 9 parts by weight of (A) and 10 to 9 parts by weight of (B).
0 parts by weight, preferably (A) 70 to 30 parts by weight, and (B) 30 to 70 parts by weight. When the amount of the polycarbonate resin (A) exceeds 90%, weather resistance,
Extrudability deteriorates, 90% PMMA of component (B)
If it exceeds, impact resistance and heat resistance decrease.

The impact modifier of component (C) is preferably a graft copolymer obtained by graft copolymerizing other components in the presence of a rubbery polymer, and more preferably AB.
Examples include S resin, AES resin, AAS resin, MBS resin, and acrylic rubber.

In the component (C), the composition ratio of each component constituting each component is not particularly limited, and each component is blended according to the use. The method for producing the copolymer of the component (C) is not particularly limited, and a generally known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization is used. Further, it can be obtained by blending separately copolymerized resins.

The resin composition of the present invention may contain, in addition to the above components, other additives, such as pigments, according to the purpose, at the time of mixing and molding the resin, as long as the physical properties are not impaired. Dye, reinforcing agent (glass fiber, carbon fiber, talc, etc.), filler (carbon black, silica, titanium oxide, etc.), heat resistant agent, antioxidant, weathering agent, lubricant, mold release agent, crystal nucleating agent, plastic Agents, flow improvers, antistatic agents,
Flame retardants and the like can be added.

Hereinafter, the present invention will be described with reference to examples.
The present invention is not limited to these.

Component (A) polycarbonate resin: polycarbonate of bisphenol A, trademark Lexan 141,
Made by Nippon GE Plastics Co., Ltd. In the following, PC
Abbreviated.

Component (B) Polymethyl methacrylate resin: Trademark MH, manufactured by Sumitomo Chemical Co., Ltd. PMMA
Abbreviation.

Component (C) Acrylic rubber: trade name Paraloid EXL2315, manufactured by Kureha Chemical Industry Co., Ltd. Abbreviated as acrylic rubber.

Examples 1 to 3 PC / PMMA resin Each component was mixed at the ratio (weight ratio) shown in Table 1 and
The mixture was extruded with a twin-screw extruder (30 mm) set at 150 ° C. and 150 rpm to form pellets. Next, the pellets were injection molded at a set temperature of 250 ° C. and a mold temperature of 60 ° C. The notched Izod impact strength (NII), heat distortion temperature (HDT), and weather resistance (ΔE) of the obtained molded product were measured. Table 1 shows the results.

Comparative Example 1 PVC resin Commercially available PVC resin: trade name RB54424, manufactured by Denki Kagaku Kogyo Co., Ltd., injection molding at a set temperature of 180 ° C. and a mold temperature of 50 ° C. The heat distortion temperature and weather resistance were measured. Table 1 shows the results.

[0041]

[Table 1]

Details of Measurement Items Notched Izod Impact Strength Measured according to ASTM-D-256 at a thickness of 3.2 mm and notched at 23 ° C. ○ Heat deformation temperature According to ASTM-D-256, a test piece having a thickness of 6.4 mm was used and measured under a load of 4.6 kg. ○ Weather resistance The degree of discoloration (ΔE) after irradiation for 2000 hours was measured using a sunshine weather o-meter.

As can be seen from the above results, the composition obtained by combining the polycarbonate resin and the polymethyl methacrylate resin has superior impact resistance and heat resistance as compared with PVC.
Weather resistance can be obtained.

Next, the extrusion moldability according to claim 4 will be described. Extrusion molding is generally used to produce thin-walled, large-area materials such as sheets. The performance required for the material is to exhibit low melt viscosity in a region where the shear rate is high and to have a high shear rate dependence in which the melt viscosity increases in a region where the shear rate is low. This makes it easier to obtain the shape of the product, and it is possible to maintain it.

By applying the material according to the present invention, when the polycarbonate resin is used alone, it exhibits extremely excellent properties such as impact resistance, heat resistance, etc., but in terms of extrusion moldability. Since the shear rate dependence is small and the processing temperature cannot be lowered so much, drawdown tends to occur and it is difficult to obtain a desired shape.

On the other hand, polymethyl methacrylate resin has excellent weather resistance, is known as a sheet material, and is used for many purposes. However, the impact strength represented by a notched Izod is very brittle and is difficult to use for products having sharp edges such as siding.
The comparison between the physical properties of these materials alone and the material of the present invention will be described below.

[0046]

[Table 2] (PC / PMMA uses data of Example 2 in Table 1)

The relationship between the shear rate of PC and PMMA and the melt viscosity is as shown in FIG.

[0048]

As is clear from the examples, the resin composition according to the present invention is excellent in impact resistance, heat resistance, weather resistance and extrudability, so that it can be applied to a wide range of applications. Be expected.

[Brief description of the drawings]

FIG. 1 is a graph showing a comparison of characteristics between a polycarbonate resin (PC) and a polymethyl methacrylate resin (PMMA) and a PC / PMMA resin composition according to the present invention.

Claims (4)

[Claims] (A) a polycarbonate resin 90 to 10
Parts by weight and (B) polymethyl methacrylate resin
90 parts by weight of the resin composition for siding. 2. A total of 1 of the components (A) and (B)
The resin composition for siding according to claim 1, wherein the composition comprises 1 to 50 parts by weight of the impact modifier (C) based on 00 parts by weight. 3. The composition according to claim 1, wherein said component (C) is ABS, AES, A
The siding resin composition according to claim 1, wherein the resin composition is at least one component selected from the group consisting of AS, ACS, MBS, and acrylic rubber. 4. A siding material obtained by processing and producing the resin composition according to claim 1 by means of extrusion molding.