JP2958171B2 - Acrylic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin formed on a surface layer of a profile co-extrusion to improve the weather resistance of a profile co-extruded product such as a vinyl chloride resin used for sashes such as window frames.

[0002]

2. Description of the Related Art Conventionally, an aluminum material is generally used for a sash, and a sash using a vinyl chloride resin has been used in order to provide a degree of freedom of a surface or a shape. In such a vinyl chloride resin sash, it is known to co-extrude a resin layer containing an acrylic resin as a main component in order to supplement the weather resistance of the vinyl chloride resin.

[0003]

However, when an acrylic resin is co-extruded on the surface layer of a vinyl chloride resin or the like to improve the weather resistance, a sizing die called plate-out often adheres. Although the cause of this occurrence is not known in detail, it is considered that the resin component adheres to the metal surface for some reason during cooling. When plate-out occurs, the surface of the product is scratched by deposits, resulting in an extremely poor appearance.

Further, the following points must be considered as the acrylic resin to be used. (1) The fluidity of the acrylic resin must be matched to the fluidity of the vinyl chloride resin to some extent so that co-extrusion molding with the vinyl chloride resin is possible, and it is necessary to select a resin composition. (2) In order not to reduce the impact resistance of vinyl chloride resin,
The impact resistance of the acrylic resin is required, and the addition of an acrylic resin-based multilayer elastic body is required. In general, when such a multilayer elastic body is added, the fluidity is reduced, and the co-extrusion with a vinyl chloride resin is deteriorated.

[0005]

SUMMARY OF THE INVENTION The present invention relates to an acrylic co-extrusion molding of an acrylic resin based on a vinyl chloride resin or the like, in which the occurrence of plate-out is suppressed and the above-mentioned two points are balanced. It is intended to provide a resin composition.

That is, the present invention comprises 80 to 100% by weight of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms and 0 to 20% by weight of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, Polymer 0.1
g) dissolved in 100 cc of chloroform, and 80 to 30 parts by weight of an acrylic copolymer (I) having a reduced viscosity [η] _{SP / C} of 0.1 l / g or less measured at 25 ° C., and an acrylic resin as a main component. 100 parts by weight of a resin composition obtained by mixing 20 to 70 parts by weight of a multilayer structure polymer (II) to be produced, is 1 to 20 parts by weight of crosslinked fine particles (III) having an average particle diameter of 1 to 20 μm containing methyl methacrylate as a main component The present invention relates to a partially mixed acrylic resin composition.

Hereinafter, the present invention will be described in detail. As the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms in the acrylic copolymer (I) of the present invention, methyl methacrylate is most preferable, and 1 to 8 carbon atoms are preferable.
Examples of the alkyl acrylate having an alkyl group include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. Can be The ratio of the alkyl methacrylate to the alkyl acrylate is from 80 to 100
The alkyl acrylate is 0 to 20% by weight based on the weight%. Alkyl acrylate 20% by weight
If it exceeds, mechanical properties such as strength and elongation may be reduced,
Heat resistance is greatly reduced.

The acrylic copolymer (I) is prepared by dissolving 0.1 g of the polymer in 100 cc of chloroform so that the reduced viscosity [η] _{SP / C} measured at 25 ° _C. becomes 0.1 l / g or less. It is important that when the reduced viscosity exceeds 0.1 l / g, the fluidity decreases, and when mixed with the multilayer polymer (II), the fluidity decreases.

Next, the multi-layer polymer (II) used in the present invention is a component for imparting impact resistance and elongation to the resin composition, and uses an alkyl acrylate as a rubber component. For example, a polymer having a multilayer structure having a two-layer structure as disclosed in JP-B-54-18298, and a polymer having a three-layer structure as disclosed in JP-A-62-230841.
Layer-structured polymers, and furthermore, those disclosed in JP-A-57-140161 and JP-A-52-56150.
Layered polymers and the like can be used.

In the present invention, the acrylic copolymer (I)
The mixing ratio of the acrylic polymer (II) and the multilayer polymer (II) is extremely important when co-extrusion molding with a vinyl chloride resin is carried out. It is necessary to mix 20 to 70 parts by weight of II). When the amount of the acrylic copolymer (I) is less than 30 parts by weight and the amount of the multilayer structure polymer (II) exceeds 70 parts by weight, the fluidity is reduced, so that coextrusion molding with a vinyl chloride resin becomes difficult.
On the other hand, when the amount of the acrylic copolymer (I) exceeds 80 parts by weight and the amount of the multilayer structure polymer (II) is less than 20 parts by weight, the impact strength of the co-extruded product with the vinyl chloride resin decreases, and the product is damaged. It will be easier.

It is known that plate-out often causes a problem even when molding vinyl chloride resin, and it is known that it can be dealt with by using a high molecular weight lubricant. Even if such a high-molecular lubricant was added to the product, the stain on the sizing die, that is, the plate-out could not be eliminated. Also, it is known that adding a specific matting agent to improve plate-out is effective.However, it is necessary to add a large amount of matting agent, and as a result, products with a matte surface I could only get it. However, according to the present invention, it has been found that plate-out can be eliminated by adding a small amount of crosslinked fine particles having an average particle size of 1 to 20 μm mainly composed of an acrylic resin.

The crosslinked fine particles (III) of the present invention contain an alkyl acrylate or an alkyl methacrylate as a main component since the transparency and the coloration are easily maintained when the refractive index is matched with the resin composition as the base material. However, an aromatic vinyl compound such as styrene or substituted styrene may be used in combination. As the crosslinking agent, a polyfunctional monomer such as divinylbenzene, trivinylbenzene, or alkylene glycol diacrylate is used, and one type can be used alone or two or more types can be used in combination. The amount of the crosslinking agent used is 2 to 50% by weight, preferably 5 to 20% by weight.
It is. It is preferable that the crosslinked fine particles (III) do not lose their shape due to heat or kneading during co-extrusion molding or have a large effect on the fluidity of the base resin. It is desirable to raise. The average particle size of the crosslinked fine particles (III) needs to be 1 to 20 μm. When the average particle size is less than 1 μm, the average particle size is close to the average particle size of the multilayer structure polymer, and the effect of plate-out is small.

The crosslinked fine particles (III) are a resin composition 1 comprising an acrylic copolymer (I) and a multilayer structure polymer (II).
1 to 20 parts by weight, preferably 3 to 1 part by weight with respect to 00 parts by weight
0 parts by weight are added. The amount of crosslinked fine particles (III) added is 1
Plate-outs of less than parts by weight are not resolved, while 2
If the amount exceeds 0 parts by weight, the properties of the base resin composition, such as fluidity and impact resistance, are impaired, and the matte state of the surface becomes too strong.

The acrylic resin composition of the present invention can be colored. A general coloring agent may be added, or the crosslinked fine particles themselves may be colored.

[0015]

The present invention will be described in more detail with reference to the following examples. The evaluation of physical properties in the examples was performed according to the following methods. The heat distortion temperature (HDT) was measured according to ASTM D-648. Vicat softening temperature (VST) is ASTM D-1
525. Izod impact strength (Iz) is ASTM D-2
Performed according to 56. Melt index (MI) is ASTM D-1
238.

(1) An acrylic resin (Acrypet MF: manufactured by Mitsubishi Rayon Co., Ltd.) comprising 87% by weight of methyl methacrylate and 13% by weight of methyl acrylate is prepared as the acrylic copolymer (I). did. [Η] _{SP / C} = 0.051 l / g HDT = 80.0 ° C. VST = 95.0 ° C. Iz = 1.60 kg · cm / cm ²

(2) A multilayer polymer (II) was produced by the following method. (1) First-stage production First, the following raw material (i) was placed in a stainless steel reaction vessel having an inner volume of 50 liters, and the monomer mixture (A-1) 802. 4 g at a time, nitrogen gas was blown into it to make it substantially free of oxygen, the temperature was raised to 70 ° C., the following raw material (ii) was added, polymerization was carried out for 60 minutes, and then Table 1 (A
1203.6 g of the monomer mixture of -2) was added continuously over 30 minutes to polymerize, and after the addition was completed, 90
The polymerization was continued for minutes. (I) Raw material Deionized water 25 kg N-lauroyl sarcosine sodium 8 g (hereinafter referred to as “S-LN”) boric acid 100 g sodium carbonate 10 g ferrous sulfate 0.01 g ethylenediamine-4-acetic acid-2-sodium 0.04 g ( (Hereinafter referred to as “EDTA-2Na”) (ii) Raw material deionized water 500 g sodium-formaldehyde sulfoxylate 40 g (hereinafter referred to as “Rongalit”)

[Table 1] BS: butyl acrylate ST: styrene MMA: methyl methacrylate C ₄ -DA: 1,4-butanediol dimethacrylate t-BH: tertiary butyl hydroperoxide (2) Second stage production Obtained in (1) above 500 kg of deionized water was placed in the same container containing 2 kg of the polymer solid part of the semi-soft crosslinked resin of the first stage.
g and 50 g of (S-LN) and 20 g of (Rongalit) were added, and the internal temperature was raised to 80 ° C.
81% of butyl acrylate, 17.5% of styrene, triallyl isocyanurate (hereinafter abbreviated as "TAIC")
1.1%, 1,4-butanediol diacrylate (hereinafter, referred to as "C ₄ -DA") consisting of 0.4% crosslinked acrylic acid ester monomer mixture (B) 8 kg to tertiary Ryi-butyl hydroperoxide Peroxide (hereinafter referred to as “t-B
H)) and polymerized while continuously adding over a period of 150 minutes.
The polymerization was continued for 80 minutes. Then, a second-stage latex of an elastomer layer containing the first-stage resin inside the particles was obtained. The polymer particle diameter of the latex at the end of the second step was measured by an absorbance method and found to be 0.28 μm. (3) Third-stage production Two different stages of the first and second stages obtained in (2) above.
80 g of deionized water and 40 g of (S-LN) were added to the same container containing 10 kg of the polymer solid content of the copolymer latex having the step structure, and stirred at 80 ° C.
While maintaining the internal temperature, a monomer mixture (C) consisting of 6 kg of a mixture consisting of 95% of methyl methacrylate and 5% of methyl acrylate, 13.8 g of normal octyl mercaptan and 9 g of t-BH at a rate of 40 parts / hour. Added continuously. Thereafter, polymerization was continued for another hour. Then, a multi-structure polymer (II) was obtained in the form of a latex. The polymerization rate of the monomer mixture (C) was 99.5% or more. The latex was coagulated, washed and dried to obtain a powder by the method described below. 100 kg of 1.0% sulfuric acid in a stainless steel container
The temperature was raised to 70 ° C. under stirring, and 40 kg of the latex previously produced was continuously added over 15 minutes.
Thereafter, the internal temperature was raised to 90 ° C. and maintained for 5 minutes. After cooling to room temperature, the polymer was separated by filtration and washed with deionized water to obtain a white creamy polymer, which was dried at 70 ° C. for 24 hours to obtain a white powdery polymer.

(3) The following were prepared as crosslinked fine particles (III). Crosslinked fine particles 1 Crosslinked fine particles having an average particle diameter of 8 μm crosslinked with 3.5% 1,6-hexanediol dimethacrylate at 100% by weight of methyl methacrylate: Techpolymer MBX-8 (manufactured by Sekisui Chemical Co., Ltd.) Crosslinked fine particles 2 Crosslinked fine particles having an average particle size of 2 μm with 100% by weight of methyl methacrylate: MR-2G (manufactured by Soken Chemical Co., Ltd.) Crosslinked fine particles 3 Crosslinked fine particles having an average particle size of 7 μm with 100% by weight of methyl methacrylate: MR-7G (manufactured by Soken Chemical Company Crosslinked fine particles 4 Crosslinked fine particles having an average particle diameter of 13 μm with 100% by weight of methyl methacrylate: MR-13G (manufactured by Soken Chemical Co., Ltd.) Crosslinked fine particles 5 Crosslinking with 100% by weight of methyl methacrylate colored with carbon black and having an average particle diameter of 12 μm. Fine particles: Techpolymer MBX-8 (manufactured by Sekisui Chemical Co., Ltd.) Crosslinked fine particles 6 Commercially available MBS resin: Metablen F410 Mitsubishi Rayon Co., Ltd. products)

Examples 1 to 3 and Comparative Examples 1 to 4 After kneading the acully copolymer (I), the multilayered elastic body (II) and the crosslinked fine particles (III) at the ratios shown in Table 1,
The sample was manufactured by the extruder. Table 1 shows the measurement results of the melt index and Izod impact strength. In addition,
In Examples 1 to 3, the balance between the melt index and the Izod impact strength was balanced, and no bleed-out occurred due to the addition of the crosslinked fine particles. In Comparative Examples 1 to 3, the fluidity was good but the Izod impact strength was low. In Comparative Example 4, the fluidity was significantly reduced, and co-extrusion molding became difficult.

[0020]

[Table 1]

Examples 4 to 11, Comparative Examples 5 to 7 68 parts by weight of acrylic copolymer (I), 32 parts by weight of multilayered elastic body (II) and crosslinked fine particles (III) shown in Table 2
) And a resin composition obtained by mixing 1 part by weight of carbon black except for Examples 10 and 11 was co-extruded with a vinyl chloride resin. The molding temperature of the acrylic resin composition was 210 ° C, and the molding temperature of the vinyl chloride resin was 190 ° C. The average thickness of the acrylic resin layer was 0.2 mm. Table 2 shows the state of occurrence of plate out of the obtained co-extruded plate. From the results in Table 2, it was found that the addition of the crosslinked fine particles containing methyl methacrylate as a main component as in Examples 4 to 9 was effective in plate-out at a lower addition amount than Comparative Examples 5 to 7, It can be seen that in Example 7, although the plate-out effect was obtained, the matting of the surface was considerably increased.

[0022]

[Table 2]

[0023]

Industrial Applicability The acrylic resin composition of the present invention can be deformed and coextruded with a vinyl chloride resin while suppressing the occurrence of plate-out, and the molded product can maintain the impact strength. Has great significance.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B29K 33:00 (56) References JP-A-63-77963 (JP, A) JP-A-59-102947 (JP, A) JP-A-63-199258 (JP, A) JP-A-59-86650 (JP, A) JP-A-61-192759 (JP, A) JP-A-60-69153 (JP, A) JP-A-60-65051 (JP, A) JP, A) JP-A-62-285942 (JP, A) JP-A-62-275147 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 33/04-33/12 C08L 51/06

Claims (1)

(57) [Claims] 1. A polymer comprising 80 to 100% by weight of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms and 0 to 20% by weight of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms. .1 g in 100 cc of chloroform and reduced viscosity [η] measured at 25 ° C.
Acrylic copolymer (I) having _{SP / C} of 0.1 l / g or less
80 to 30 parts by weight and 100 to 100 parts by weight of a resin composition obtained by mixing 20 to 70 parts by weight of the multilayer polymer (II) containing acrylic resin as a main component have an average particle size of methyl methacrylate of 1 as a main component. 1 to 20 μm crosslinked fine particles (III)
An acrylic resin composition mixed with 20 parts by weight.