JPS60217250A - Vinyl chloride resin sheet - Google Patents

Abstract

PURPOSE:A sheet, obtained by molding a kneaded material of a specific polyester polyol with a vinyl chloride resin, and slightly hardening with time without discoloration nor deterioration by sunlight, heat and CO2 nor migration to adhesives, etc. CONSTITUTION:A vinyl chloride resin sheet obtained by kneading a polyester polyol, prepared by polymerizing a 4-7 membered ring lactone in the presence of a bi-or polyfunctional condensation based polyester having terminal hydroxyl groups and 1,000-7,000 molecular weight as an initiator, and having 10,000- 100,000 molecular weight with a vinyl chloride resin, and molding the knead material. The mixing weight ratio of the polyester polyol to the vinyl chloride resin is 100:80-100:200.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin sheet, and more specifically, it is stable against discoloration and deterioration due to sunlight, heat, and nitrogen dioxide gas, and has good migration properties to adhesives, etc. 1. This invention relates to a vinyl chloride resin sheet suitable for applications such as automobile stickers.

Conventionally, there are many plasticizers used in vinyl chloride resins, such as phthalate esters, aliphatic polyesters, and epoxy compounds, but the most commonly used one is -DOP ( phthalic acid derivatives including dioctyl phthalate). Although these phthalate esters have excellent plasticizing performance, they have defects such as high extractability and migration, and are easily extracted by gasoline and oil, making them unsuitable as materials for automobile exterior parts. 0 Also, if vinyl chloride resin containing these phthalate esters is left in contact with other synthetic resins, the plasticizer will migrate from the vinyl chloride resin to the other resins. This often causes deterioration or deterioration of the resin, and especially in sticker sheets for automobiles, it causes deterioration of the adhesive and peeling of the sheet.

Furthermore, vinyl chloride resin containing phthalate ester
Due to its small retention property, sunlight, heat, and nitrogen dioxide gas accelerate its volatilization, which can easily cause discoloration and deterioration.On the other hand, in order to solve problems such as plasticizer migration, various conventional methods have been used. It is already known that a vinyl chloride/u resin composition having excellent mechanical strength, extraction resistance, oil resistance, cold resistance, etc. can be obtained by blending molecular weight polycaprolactone with vinyl chloride resin.

However, the conventionally used polycaprolactone mentioned above is linear, and even if it is branched, it has a low molecular weight. Therefore, due to the strong crystallinity of polycaprolactone, it is difficult to be oriented. Immediately, when a vinyl chloride resin sheet was used, a large change over time appeared, and the stability of the physical properties was not satisfactory. The present inventors developed a special polycaprolactone in order to eliminate the above-mentioned drawbacks of the conventional sheet. However, by mixing a specific amount of this polycaprolactone with vinyl chloride resin, it is possible to create a polycarbonate that has extremely good compatibility, good migration resistance, does not change or deteriorate due to sunlight, heat, nitrogen dioxide gas, and has little curing over time. The present invention was achieved by discovering that a vinyl chloride resin composition can be obtained. That is, the present invention provides for rings with 4 to 7 ring members.
The lactones have a molecular weight of i, ooo to 7.
000 condensed polyester as an initiator and a polyester polyol having a molecular weight of 10,000 to 100,000, and a vinyl chloride resin. .

The lactones having 4 to 7 ring members used in the present invention include lactones having 4 to 7 ring members with or without one or more methyl groups as a substituent, such as β-propiolactone, bivalolactone, δ -valerolactone, ε-
Caprolactone, methyl-ε-caprolactone, ? Examples include methyl-ε-caprolactone and trimethyl-ε-caprolactone.

In addition, the trifunctional or higher functional compound used in the present invention has a molecular weight of 1,000 to 7.
,000 condensation polyester is obtained by polycondensing a diol and a dicarboxylic acid or an oxycarboxylic acid. Examples of diols used in the present invention include alkylene diols having 2 to 10 carbon atoms without a side chain, diols having 3 to 8 carbon atoms having a methyl group in the side chain, such as 1,2-glopylene glycol, 1,3- phthylene glycol, -y-l, neopentyl glycol,
The use of these diols is essential in order to provide a substantially linear polyester diol, but polyhydric alcohols such as trimethylolpropane and pentaerythritol may also be used as long as they do not cause gelation. The dicarboxylic acid may be used in combination with the diol during the production of the polyester diol. Also, as the dicarboxylic acid, saturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms without side chains, such as succinic acid, geltaric acid, adipic acid, pimelic acid, Speric acid, azelaic acid, sebacic acid, undecane dioic acid
acid), dodecane
dioic acid), etc. are used. In addition, methyl adipic acid, dimethyl adipic acid, etc. are used. Unsaturated dicarboxylic acids or their acid anhydrides can also be used.For example, polybasic acids such as tricarboxylic acids and tetracarboxylic acids can also be used in conjunction with unsaturated dicarboxylic acids having 4 to 5 carbon atoms. It may be used as long as it does not cause any adverse effects.

Next, as the oxycarboxylic acid, ω-hydroxyalkanoic acids having 2 to 6 carbon atoms such as glycolic acid are used.
99.9% by weight and 0.1 to 3 monomers copolymerizable with this
0% by weight.

Examples of monomers that can be copolymerized with vinyl chloride include vinyl acetate, vinylidene chloride, acrylonitrile, diethyl maleate, dibutyl maleate, diethyl fumarate, methyl acrylate, ethyl acrylate, methyl methacrylate, butyl methacrylate, and the like.

Molecular weight used in the present invention: 10,000 to ioo, ooo
The mixing weight ratio of Nofuri ester polyol and vinyl chloride resin is 100:80 to Zoo:200.

In order to produce the resin hybrid of the present invention from the polyester polyol having a molecular weight of 10,000 to 100,000 and vinyl chloride resin, the mixture is heated and kneaded using a mixing roll, an extrusion molding machine, or the like. The obtained mixed wire material is molded into a sheet shape by a molding process such as hot pressing or calendering.

In addition, the resin kneaded product of the present invention may contain stabilizers,
Fillers, colorants, lubricants, chemical foaming agents, etc. can be added.

The vinyl chloride resin sheet of the present invention does not have the problem of plasticizer migration compared to a vinyl chloride resin with a plasticizer added thereto, and is excellent in discoloration and deterioration caused by sunlight, heat, and nitrogen dioxide.

In addition, compared to a polyvinyl chloride resin blended with linear low-molecular-weight polycaprolactone, it is superior in discoloration and deterioration caused by sunlight, heat, and nitrogen dioxide, and its physical properties change less over time.

Therefore, the vinyl chloride resin composition of the present invention can be used as a material for automobile interior and exterior parts such as automobile sticker sheets, where change and deterioration due to sunlight, heat, nitrogen dioxide, and migration to adhesives are problematic. Extremely effective.

The present invention will be specifically explained below using Examples.

Parts in the examples are based on parts by weight.

In each physical property in the examples, 100% modulus, tensile elongation, 0 light resistance measured according to Jl:S-6723 at a tensile speed of 200'X/min,
The zero heat resistance was measured by measuring the tensile strength retention after 100 hours at a panel temperature of 63°C using a fade-o-meter, and the elongation retention after being left in a gear oven at 100°C for 120 hours.

The oxidation gas resistance test was carried out according to the LIS-L-0855 nitrogen oxide gas exposure test by polycondensing 9.8 moles of 1.3 butanediol and 9 moles of adipic acid. Molecular weight: 2,550 Acid value: 1.
227 parts of this polyester was used as an initiator to obtain the polyester of No. 1, and 890 parts of E-caprolactone was added to it.
part of catalyst (
diphenyltin dilaurate) and heated to 150°C to 20°C.
The reaction was allowed to proceed at 0° C. for 14 hours, and unreacted substances were distilled off under reduced pressure for an additional hour to obtain polycaprolactone A having a molecular weight of about 13,000 and an acid value of 0.5.

Next, 88 parts of the polycaprolactone, degree of polymerization 1.05
100 parts of vinyl chloride resin, 1 part of barium stearate
．． 3 parts of zinc stearate and 1.3 parts of zinc stearate were kneaded for 12 minutes on a heated roll at 165°C.The resulting mixed wire was further placed in a hot press at 175°C and hot pressed for 5 minutes at a pressure of 200 Jr9/crA. A test sheet with a thickness of about [■] was obtained.゛The light resistance, heat resistance, and nitrogen oxide gas resistance of the obtained test sheet were measured for changes in physical properties over time. The results were as shown in Table 0. Examples 2 to 3 65% of polycaprolactone A obtained in Example 1, respectively.
Part, Sekibe Tori, Vinyl chloride resin with a degree of polymerization of 1,050 10
0 parts, 1.3 parts of calcium stearate, and 1.3 parts of zinc stearate were kneaded for 12 minutes on a heated roll at 165°C. The obtained mixed wire was further placed in a heat press at 175°C and heat pressed for 5 minutes at a pressure of 2 mm/y to obtain a test sheet with a thickness of approximately 1 m+n.The obtained test sheet was evaluated for light resistance and The changes in heat resistance and oxidation gas resistance physical properties over time were measured and the results are shown in Table 1.

Example 4 A polyester having a molecular weight of 5.10 parts and an acid value of 0.7 was obtained by polycondensing 4.86 moles of 1.3 butanediol, 3.24 moles of 1.6 hexanediol, and 7.5 moles of adipic acid. Ta. As an initiator, 444 parts of the previously obtained polyester was taken, 870 parts of ε-caprolactone was added thereto, and a catalyst (0.1% of the total weight of the formulation) was added.
Tetrabutyl titanate) was added and reacted at 150 to 200°C for 13 hours, and unreacted substances were distilled off under reduced pressure for another 1 hour.
Molecular weight 15,000. Polycaprolactone B with an acid value of 0.6 was obtained. Next, 880 parts of the polycaprolactone and a degree of polymerization of 1.0 were added.
100 parts of vinyl chloride resin of 50, 1.3 parts of barium stearate and 1.3 parts of zinc and lead stearate were added to 165
The mixture was kneaded for 12 minutes on heated rolls at . Below, Example 1
A test sheet was prepared in the same manner as above, and the physical properties were measured. The results were as shown in Table 1. ,,.

Example 5 9.07 mol of neopentyl glycol and 8 mol of sebacic acid
．． By polycondensing 4 moles, the molecular weight is 3,900.
A polyester having an acid value Q of 9 was obtained.

As an initiator, take 120 parts of the polyester obtained above, add ε-caprolactone to it, add 246 parts of ε-caprolactone, and further add 0.1% of a catalyst (diptyltin diacetate) based on the total weight of the mixture to give 150 parts of the polyester obtained above. The reaction was carried out at ~120°C for 14 hours, and unreacted substances were distilled off under reduced pressure for another hour, resulting in a molecular weight of about 11,
900 to obtain polycaprolactone C with an acid value of 0.8. Next, 080 parts of the polycaprolactone and a degree of polymerization of 1.0 were obtained.
A test sheet was prepared in the same manner as in Example 1 by kneading 100 parts of vinyl chloride resin No. 50, 1.3 parts of barium stearate and 1.3 parts of zinc stearate on a heated roll at 165°C for 12 minutes. Physical properties were measured. The results were as shown in Table 1. Comparative Examples 1 to 4 80 parts each of DOP, DOA, epoxidized soybean oil, and polyester plasticizer were taken and the polymerization degree was 1,050.
100 parts of vinyl chloride resin, 1 part of calcium stearate
．． 3 parts and 1.3 parts of barium stearate and 1.3 parts of zinc stearate.
The mixture was kneaded for 0 minutes. The obtained kneaded product was further placed in a hot press at 175°C and hot pressed for 5 minutes at a pressure of 200 #/c4 to obtain a test sheet with a thickness of about 1 cylinder. Physical properties were measured in the same manner. The result is -
Comparative Example 5: Using 4.25 parts of ethylene glycol as an initiator, 150 parts of dimethyl-ε-caprolactone was added to the initiator, and further a catalyst (calcium methoxyrad) -O,OS part was added. 1
The reaction was carried out at 50 to 200°C for 72 hours, and unreacted substances were distilled off under reduced pressure for another hour to obtain polycaprolactone D having a molecular weight of 2,220 and an acid value of 2.9.

Next, 080 parts of the polycaprolactone, degree of polymerization 1.0
100 parts of vinyl chloride resin No. 50, 1.3 parts of barium stearate, and 1.3 parts of zinc stearate were kneaded for 12 minutes on a heated roll at 165°C. Thereafter, a test sheet was prepared in the same manner as in Example 1, and its physical properties were measured. The results were as shown in Table 1.

Table - Change 20...Change representation, ○...Slight discoloration, Δ
...Kana] Yellowing note) 1) Polyester plasticizer: average molecular weight 2,000, manufactured by Dainichiseika Industries Co., Ltd. 2) Ioo% modulus ... Jl: 5K6
723.

3) Tensile strength: According to JIS K6723.

4) Elongation: According to JISK6723.

5) Light resistance...Fade-o-meter 63℃
100 hours 6) Heat resistance...100℃ 120 hours 7) Oxidation gas resistance... after 5 units Patent applicant: Dainichiseika Kagyo Co., Ltd. Ukima Gosei Co., Ltd.

Claims (1)

[Claims] 1. Lactones having 4 to 7 ring members, with a hydroxyl group at the end, a molecular weight of 2 or more, and a molecular weight of i, o o o to 7.00.
Resistant to discoloration and deterioration due to sunlight, heat, and nitrogen dioxide by molding a polyester polyol with a molecular weight of io, ooo to 100,000 obtained by polymerizing a condensed polyester of 0.0 as an initiator and a vinyl chloride resin. PVC resin sheet that is stable against