JP2000281854A - Rigid molding product for vinyl chloride-based building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rigid molding product for a building material comprising a vinyl chloride-based resin composition as a molding product, not lowering bond strength between a silicone sealant and the surface of the molding product and not changing sealing effect even for a long period of time hours after the silicone sealant is bonded to the surface of the molding product and the molding product is applied. SOLUTION: This rigid molding product comprises a vinyl chloride-based resin composition as a molding material composed of (a) a vinyl chloride-based resin, (b) a filler having >=70 wt.% SiO2 content ratio and (c) a stabilizer. The vinyl chloride-based resin composition is further formulated with (d) an acrylic resin and (e) a thermal decomposition type blowing type agent to give a vinyl chloride-based resin composition, which is used as a molding material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard molded article for a vinyl chloride resin building material which has excellent physical properties and appearance and has sufficient adhesive strength with a silicone sealant during construction.

[0002]

2. Description of the Related Art Conventionally, rigid molded articles of vinyl chloride resin have been widely used for building materials such as window frames, pipes, joints, bench materials, synthetic wood, etc. because of their excellent mechanical strength, flame retardancy and weather resistance. Have been. Among vinyl chloride resin hard molded products,
The foam molding method (Celca molding method) developed by Eugene Coolman in France is known, and the low foam molded product obtained by this method has a thick skin layer (unfoamed layer) on the surface. It is characterized by. This molded article has excellent heat insulating effect, is relatively light, and has a smooth molded article surface, so that it is used in a wide range of fields as bench materials, hollow deformed pipes, window frames, and the like.

[0003]

In general, when these molded products are used as building materials, a silicone sealant is often used as a joint stopper. However, commercially available silicone sealants for vinyl chloride resin molded products may have problems such as a decrease in adhesive strength due to the surface condition and deformation of the molded product over time, causing water leakage and the like. . As one of the causes of these problems, after bonding the molded product with silicone sealant,
After a long period of time, additives such as lubricants and liquids, which are poorly compatible with the vinyl chloride resin contained in the molded product, bleed to the surface of the molded product, so that the adhesive strength between the silicone sealant and the surface of the molded product is reduced. It is thought to decrease. As a method of improving the adhesive strength, it is effective to reduce the amount of the lubricant in the vinyl chloride resin composition and the amount of the liquid material. Problems often occur during molding, such as stagnation due to stagnation and plate-out at the die portion.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and have reached the present invention. That is, the present invention provides: (a) 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 500 to 1,700; (b) 1 to 20 parts by weight of a filler having an SiO ₂ content of 70% by weight or more; It is a hard molded article for a vinyl chloride resin building material using a vinyl chloride resin composition containing up to 10 parts by weight as a molding material, and the vinyl chloride resin composition further comprises (d) a concentration of 0.1 dl / 100 ml chloroform. 3.0dl reduced viscosity measured at 20 ℃ using solution
/ g or more acrylic resin 0.1 to 30 parts by weight and (e)
It is a hard low-foaming molded article for building materials using a vinyl chloride resin composition to which 0.01 to 10 parts by weight of a pyrolytic foaming agent is added as a molding material.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The average degree of polymerization of the vinyl chloride resin in the present invention is 500 to 1,
It must be in the range of 700 and the average degree of polymerization is 500
If the average polymerization degree is less than 1,700, the melt viscosity of the vinyl chloride resin at the time of molding becomes high, and the melt viscosity of the molded article obtained by extrusion molding or injection molding is inferior. Good molded products cannot be obtained.
Specifically, in injection molding, the melt viscosity becomes too high, the injection resistance increases, and the molded product becomes unfilled.In particular, when the set temperature of the molding machine is raised for the purpose of lowering the melt viscosity, vinyl chloride is used. Decomposition of the system resin occurs, so-called silver is generated, and a good molded product cannot be obtained, which is not preferable. Further, if the melt viscosity of the vinyl chloride resin becomes too high in extrusion molding, especially foam extrusion molding, the surface properties of the obtained molded product and the state of the foamed cells become non-uniform, and the moldability is significantly reduced. Therefore, preferably the average degree of polymerization is
It is preferable to use 600 to 1,300 vinyl chloride resins.

The vinyl chloride resin used as the component (a) in the present invention contains at least 50% by weight of vinyl chloride, a vinyl chloride homopolymer, vinyl chloride and a vinyl copolymerizable monomer. It is a vinyl chloride copolymer. Examples of such a monomer copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters such as methyl acrylate and ethyl acrylate; and methyl methacrylate and ethyl methacrylate. Methacrylic acid esters; olefins such as ethylene and propylene; acrylonitrile;
And vinylidene chloride.

The amount of the component (b) used in the present invention
Is 1 to 100 parts by weight of the vinyl chloride resin of component (a).
-20 parts by weight, preferably 4-17 parts by weight, more preferably 8 parts by weight
~ 15 parts by weight, which is 1 part by weight
If less, the effect of improving the silicone peel strength of the molded product is not
If it is sufficient and exceeds 20 parts by weight,
Physical properties such as impact resistance and tensile elongation of molded products obtained by
Is not preferred. Used as component (b) in the present invention
SiO₂As the filler contained, the above-mentioned silicone
To improve the adhesive effect with the sealant,
But SiO₂Using clay, silica powder, etc. with a high content of
Is effective. SiO in filler ₂Content ratio is 70 weight
% Or less, and less than 70% by weight
The effect of improving the cone peeling load is reduced.

The amount of the component (c) used in the present invention is 1 to 100 parts by weight of the vinyl chloride resin of the component (a).
If the amount is less than 1 part by weight, it is not possible to prevent the resin from decomposing and deteriorating during extrusion molding. I can't get it. Examples of the stabilizer as the component (c) in the present invention include laurate-based, malate-based, and mercaptide-based organotin stabilizers; metal soap stabilizers such as calcium stearate, barium stearate, lead stearate, and zinc stearate; Lead-based stabilizers such as basic lead sulfate, lead silicate and dibasic lead phosphite are exemplified.

In the hard molded article material for a vinyl chloride resin building material of the present invention, (a) an average degree of polymerization of 500 to 1,70
Acrylic resin having a reduced viscosity of 1.0 dl / g or more measured at 20 ° C. using 0.1 g / 100 ml chloroform solution with respect to 100 parts by weight of vinyl chloride resin
The addition of 30 parts by weight provides the following advantages.

The acrylic resin used as the component (d) in the present invention has a reduced viscosity of 1.0 dl / g or more, preferably 1.0 to 20 dl / g, measured at 20 ° C. using a chloroform solution having a concentration of 0.1 g / 100 ml. Use something. By using the acrylic resin giving the above reduced viscosity at the above concentration, the tensile elongation of the obtained hard molded product is improved, and the surface appearance is improved. When the hard molded product is a low-foam molded product, by adding the component (d), the tensile elongation of the obtained hard molded product is improved, and not only the surface appearance is improved, but also the cell strength is improved. Even at high temperatures, there is no coalescence of pores, preventing the once formed cells from shrinking, making the pore cells fine and uniform, and raising the specific gravity of the foamed molded product to 0.35 to 0.70 g / cm ³ , preferably 0.50 to 0.70g / cm
It can be ³ . The amount of the component (d) used in the present invention must be in the range of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the vinyl chloride resin of the component (a). If the amount is less than 0.1 part by weight, the above-mentioned effects cannot be obtained. If the amount exceeds 30 parts by weight, the melt viscosity of the resin becomes too high, which impairs the shape of the molded article and decreases the rigidity of the molded article. As the acrylic resin used for this purpose, it is preferable to use a methacrylate resin such as a methacrylate polymer or a methacrylate copolymer containing 50% by weight or more of methacrylate. For example, a copolymer consisting of methyl methacrylate and an acrylic ester such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate, or a copolymer thereof. Possible copolymers are exemplified.

When the rigid molded article for a vinyl chloride resin building material of the present invention is a low-foam molded article, the vinyl chloride resin composition of (a) to (d) is further added with a vinyl chloride component (a). (E) Pyrolytic foaming agent 0.01 per 100 parts by weight of base resin
Add ~ 10 parts by weight. The amount of the component (e) used in the present invention must be in the range of 0.01 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin as the component (a). If the amount is less than 0.01 part by weight, the foaming effect of making the cells uniform or fine cannot be obtained, and if the amount exceeds 10 parts by weight, the foaming becomes remarkable, which deteriorates the surface condition of the obtained molded article, and also increases the strength. Is also undesirably reduced. The thermal decomposition type foaming agent used as the component (e) reduces the weight of the molded product itself, and adjusts the cell structure formed at the time of foam molding uniformly and finely (bubble uniforming aid). An effect of making the nail hard to break when driven into a molded article can be provided. These include azo blowing agents such as azodicarbonamide, azobisisobutyronitrile, and diazoaminobenzene, and nitroso-based blowing agents such as N, N'-dinitrosopentamethylenetetramine and N, N'-dimethyl-dinitroterephthalamide. A foaming agent or sodium bicarbonate is used. In order to achieve both a reduction in the weight of the low-foam molded article and the securing of the surface hardness of the skin layer of the molded article, it is most preferable to use sodium bicarbonate as the pyrolytic foaming agent.

The vinyl chloride resin composition, which is a molding material of the hard molded product for building materials according to the present invention, contains calcium carbonate, titanium oxide, mica, alumina, bentonite and the like, if necessary, in addition to the above components. These may be auxiliary materials when obtaining a low-foam molded article having a fine cell structure. Further, it is optional to add a stabilizing aid, a lubricant, a flame retardant, a coloring agent, an ultraviolet absorber, an antioxidant, and the like to the composition, if necessary.

[0013]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

The raw materials used are as follows. (A): Vinyl chloride resin A-1: TK-600 (Shin-Etsu Chemical Co., Ltd., trade name, average degree of polymerization 600) A-2: TK-800 (Shin-Etsu Chemical Co., Ltd., trade name, average degree of polymerization 800) A): TK-2000 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, average degree of polymerization: 2000) (b): SiO ₂ -containing filler B-1: Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd., trade name) SiO ₂ 99.7% by weight, B-2: JP-100 (trade name, manufactured by Tsuchiya Kaolin Co., Ltd.), Si
O ₂ content of 80.0 wt%, B-3: MS- P ( Nippon Talc Co., Ltd., trade name), SiO ₂
Content: 62.0% by weight, B-4: Whiten SB (trade name, manufactured by Shiraishi Calcium Co., Ltd.), not containing SiO ₂ (calcium carbonate). (C): Stabilizer Calcium stearate, butyltin mercapto stabilizer (abbreviated as tin stabilizer in the table). (D): Acrylic resin D-1: Methyl methacrylate-n-butyl acrylate copolymer, (methyl methacrylate: 80% by weight, n-butyl acrylate: 20% by weight) 0.1 g / 100 ml chloroform The reduced viscosity measured at 20 ° C. using the solution is 11.5 dl / g. D-2: Methyl methacrylate-ethyl acrylate copolymer (methyl methacrylate 80% by weight, ethyl acrylate 20
% By weight) The reduced viscosity measured at 20 ° C. using a 0.1 g / 100 ml chloroform solution was 2.0 dl / g. (E) Pyrolytic foaming agent ・ Sodium bicarbonate (manufactured by Eiwa Chemical Co., Ltd.) Other lubricants, ester wax ・ G60 (manufactured by Henkel Japan)

The details of the test method are as follows. [Physical property evaluation method] (Specific gravity of molded article) JIS K 7112 (Method A) by cutting out 2 g of sample from the whole molded article
Was used to measure the specific gravity. (Observation of Cell State of Foam Layer of Molded Article) The cell state of the foam layer portion of the molded article was observed and evaluated according to the following criteria. A: It has a fine uniform cell structure with a cell diameter of less than 1,000 microns and has a good appearance. B: The cell diameter is 1,000 microns or more, and the cells are coarse and uneven. (Tensile test) Cut out JIS No. 1 test piece (width 20mm, length 175mm, mark interval 50mm) from the molded product by milling
A tensile test was performed in accordance with JIS K 7113, and the elongation between the marked lines at the time of breaking was measured. (Evaluation of appearance of molded product) 〇: The surface is glossy and smooth overall. Δ: The surface is not glossy and a part of the surface is not smooth. ×: The surface is not glossy, and the surface is not smooth and uneven as a whole.

(Measurement of silicone peel strength)
A test piece of 50 mm square was cut out, and the two test pieces were assembled into an L-shape as shown in FIG. Excess sealant was removed, and the thickness was adjusted to 5 mm as shown in FIG. Then, the obtained L-side assembly was left at 25 ° C. and 60% humidity for 120 days, and the (A) and (B) portions of the L-shaped test piece were fixed as shown in FIG. And 180 as shown in FIG ^. Perform a tensile test by applying a load in the direction
The load when the silicone sealant of the joint stopper was broken or peeled was measured.

(Production of Compound for Extrusion Molding) (Examples 1 to 3, Comparative Examples 1 to 5) Formulations shown in Table 1
And each component of (a), (b), (c), and (d) has a capacity of 300
Add, mix, stir and mix into Super Mixer L
Was. When the temperature of the resin in the mixer reaches 120 ° C,
This is discharged into a cooling mixer with a capacity of 500 liters.
After cooling the compound obtained to 50 ° C.,
Sodium bicarbonate was added and mixed. On the other hand, 50mm
Single screw extruder (screw: L / D = 23, CR = 2.5)
Prepare a mandrel and die with an outer diameter of 40 mm on the exit side.
(Resin outlet: 50mm horizontal * 10mm vertical), opening similar to die
Sizing dies (cooling dies) and cooling tanks
We attached sequentially. Also extruded from sizing dies
Caterpillar model behind cooling tank to draw out molded products
Was installed. The above mixture is supplied to this single screw extruder.
The temperature from the cylinder to the die (extruder system)
Linder part: C₁ ~ C ₄ , Dice part: D₁ ~ D₂ )
Is set to the following temperature, and the screw speed is 30 rpm.
And pull the extruded product with a take-off machine at a speed of 0.5 m / min.
I started. However, the resin was sufficiently melted in Comparative Example 5.
To increase the temperature, increase the set temperature by 10 ° C
Was.

[0018] (set _{temperature) C 1: 90 ℃ C 2} : 110 ℃ C 3: 130 ℃ C 4: 150 ℃ D 1: 185 ℃ D 2: 180 ℃

In the sizing die, the extruded product was cooled to room temperature by circulating water. Each of the molded articles (cross section: 50 mm in width * 10 mm in length) obtained by this method had an unfoamed skin layer on the outside and a porous foamed layer on the inside. The specific gravity of the molded article, the observation of the foam cell state of the molded article, the tensile test, and the silicone peel test were performed on the obtained molded article by the above-mentioned methods. The results are shown in Table 1.

[0020]

[Table 1]

(Production of Compounds for Injection Molding) (Examples 4 to 6, Comparative Examples 6 to 10) Each component having the formulation shown in Table 2 was added to a 300 L supermixer, blended, stirred, and mixed. did. When the resin temperature in the mixer reached 120 ° C, it was discharged into a cooling mixer having a capacity of 500 L, and the obtained compound was cooled to 50 ° C. On the other hand, a 50 mm single screw extruder (screw: L / D = 23,
C. R = 2.5), a pellet die (pellet diameter 3 mmφ) and a pelletizer were sequentially attached to the outlet side, and pellets were produced by strand cutting. Extrusion conditions cylinder Zehnder setting conditions: screw rotational _{speed: 25rpm C 1 90 ℃, D} 1 185 ℃, C 2 110 ℃, D 2 180 ℃, C 3 130 ℃, C 4 150 ℃, the resulting pellet injection molding machine (IS150, manufactured by Toshiba Machine Co., Ltd.
E) Supply the barrel temperature 160 ~ 190 ℃, injection pressure 120
Injection molding was performed under the conditions of kg / cm ² and a mold temperature of 30 ° C. to form a flat plate (width 100 mm * length 50 mm * thickness 3 mm). The obtained molded article was subjected to a tensile test and a silicone peeling test by the same method as described in Example 1 for evaluating the appearance of the molded article and the results as described in Table 2.

[0022]

[Table 2]

[0023]

According to the present invention, a hard molded article for a building material using the vinyl chloride resin composition of the present invention as a molding material is bonded to the silicone sealant with a silicone sealant even after a long time has passed since the surface of the molded article was adhered with a silicone sealant. The sealing effect does not change without lowering the adhesive strength to the surface. The hard molded article for building materials using the vinyl chloride resin composition of the present invention as a molding material is suitable for sealing with a silicone sealant.

[Brief description of the drawings]

FIG. 1 shows a method for measuring silicone peel strength.

[Explanation of symbols]

 1 Test piece (molded product), 2 Silicone sealant, 3 Chuck for fixing test piece of tensile tester.

Continued on the front page F-term (reference) 4F071 AA24 AA32 AA81 AA88 AB21 AB26 AC09 AC18 AE01 AE05 AE17 AF53 AH03 BA01 BB05 BC03 4J002 BD051 BD061 BD071 BD081 BD091 BG042 BG052 BG062 DG047 EZ037 EG0 014 FD037 FD328 GL00

Claims (6)

[Claims] (A) 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 500 to 1,700; (b) 1 to 20 parts by weight of a filler having a SiO ₂ content of 70% by weight or more; Hard molded product for vinyl chloride resin building materials using a vinyl chloride resin composition containing 10 parts by weight as a molding material. 2. An acrylic resin having a reduced viscosity of 1.0 dl / g or more measured at 20 ° C. using a chloroform solution having a concentration of 0.1 g / 100 ml with respect to 100 parts by weight of the component (a). .
The hard molded article for a vinyl chloride resin building material according to claim 1, wherein the molding material is a vinyl chloride resin composition containing 1 to 30 parts by weight. 3. The hard molded article for a vinyl chloride resin building material according to claim 1, wherein the component (b) is clay or silica powder. 4. The hard molded article for a vinyl chloride resin building material according to claim 1, wherein the molded article is an extrusion molded article or an injection molded article. 5. A vinyl chloride resin composition according to claim 2, wherein a vinyl chloride resin composition containing (e) 0.01 to 10 parts by weight of a pyrolytic foaming agent with respect to 100 parts by weight of the component (a) is used as a molding material. Hard molded product for resin based building materials. 6. A hard molded article for a vinyl chloride resin building material according to claim 5, wherein the molded article is a low-foam molded article.