JP3542877B2 - Vinyl chloride resin composition - Google Patents

Description

【００１２】
［注］
１）ＺＥＳＴ１０００Ｚ、新第一塩ビ（株）、平均重合度１０５０。
２）エラスレン３０１Ａ、昭和電工（株）、非結晶性塩素化ポリエチレン、塩素含有量３０重量％、ムーニー粘度７０（ＭＳ_１＋４１００℃）。
３）ハイブレンＢ４０３、日本ゼオン（株）、メタクリル酸メチル単位約９０重量％を有する共重合体、比粘度２．０６（０．２ｇ／ｄｌクロロホルム溶液、２５℃で測定）。
４）セルユント、（株）シマダ商会、平均粒径８０μｍ、含水率５重量％。
５）Ｅ６０−Ｔ５−３、ミサワテクノ（株）、酸化チタン粒子付着木粉、酸化チタン含有量５重量％、平均粒径６０μｍ、含水率５重量％。
６）ジ−２−エチルヘキシルフタレート。
７）ステアリン酸バリウム／ステアリン酸亜鉛系熱安定剤。
８）ｎ−ブチルステアレート。
９）炭酸カルシウム、ＣＣＲ、白石カルシウム（株）製、平均粒径０．０８μｍ。
第１表の結果から、塩素化ポリエチレンを含有する実施例１〜３の本発明の塩化ビニル系樹脂組成物は、バンクのロールへの喰い込みが良好で、安定して混練することができ、得られるシートが軟質シートとして適当な引張破壊伸び及び１００％モジュラスを有することが分かる。
これに対して、塩素化ポリエチレンを含有しない比較例１の塩化ビニル系樹脂組成物は、バンクのロールへの喰い込みが不良である。実施例１の塩素化ポリエチレンの代わりに、加工助剤であるメタクリル酸エステル系樹脂を含有せしめた比較例２の塩化ビニル系樹脂組成物は、バンクのロールへの喰い込みが不良であり、さらに、比較例３のようにメタクリル酸エステル系樹脂の含有量を増しても、バンク廻りはそれ程改良されない。
【００１３】
【発明の効果】
本発明の塩化ビニル樹脂系組成物は、バンクのロールへの喰い込みが良好で、安定して混練及びシート化することができ、木質感に富んだ内装材料に適した軟質シートを得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a vinyl chloride resin composition. More specifically, the present invention relates to a vinyl chloride resin composition containing wood flour suitable for processing a soft sheet rich in woodiness.
[0002]
[Prior art]
Since wood can be repeatedly produced by photosynthesis, it has been reviewed as a rich and promising resource different from petroleum-based resins. Attempts to grow forests with fast-growing species and reduce the concentration of carbon dioxide in the atmosphere to regenerate a healthy global environment, while also systematically cutting down and using wood as a resource for human life Has been done. Under these circumstances, wood flour is blended with vinyl chloride resin, which is a general-purpose resin that has high mechanical strength and is easy to mold, and is often used for interior materials such as wall materials, ceiling materials, and floor materials. If a vinyl chloride resin composition can be developed, a harmonious use of earth resources will be greatly pioneered.
2. Description of the Related Art Conventionally, for the purpose of exhibiting an appearance and a tactile sensation similar to wood, it has been often performed to mix wood powder with a vinyl chloride resin and mold it. However, the vinyl chloride resin composition for a soft sheet containing a considerable amount of wood powder and a plasticizer has a problem in that the bank turns are poor in calendering, that is, the roll runs idle without the bank being bitten on the roll gap. And stable production was difficult.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a vinyl chloride-based resin composition that contains a large amount of wood flour and can stably produce a vinyl chloride-based resin soft sheet as an interior material with a rich woody feel. It is a thing.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by adding a chlorinated polyethylene to a composition containing a vinyl chloride-based resin, wood flour and a plasticizer, the circulation around the bank is reduced. It has been found that the kneaded material can be kneaded more stably by a roll, and based on this finding, the present invention has been completed. That is, the present invention provides (A) 100 parts by weight of a vinyl chloride resin, (B) 0.5 to 30 parts by weight of chlorinated polyethylene, (C) 15 to 150 parts by weight of wood powder having an average particle size of 50 to 500 μm, and ( D) A vinyl chloride resin composition containing 25 to 200 parts by weight of a plasticizer.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
Examples of the vinyl chloride resin used as the component (A) in the composition of the present invention include vinyl chloride homopolymers and vinyl chloride copolymers having a vinyl chloride unit of 50% by weight or more. Examples of monomers copolymerized with vinyl chloride include olefins such as ethylene and propylene; halogenated olefins such as allyl chloride, vinylidene chloride, vinyl fluoride and ethylene trifluoride chloride; vinyl acetate and propionic acid Carboxylic acid vinyl esters such as vinyl; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyl ethers such as allyl-3-chloro-2-oxypropyl ether and allyl glycidyl ether; acrylic acid, maleic acid, itaconic acid and acrylic Unsaturated carboxylic acids such as 2-hydroxyethyl acid, methyl methacrylate, monomethyl maleate, diethyl maleate and maleic anhydride, esters and acid anhydrides thereof; unsaturated nitriles such as acrylonitrile and methacrylonitrile Acrylamides such as acrylamide, N-methylolacrylamide, acrylamide-2-methylpropanesulfonic acid, and (meth) acrylamidopropyltrimethylammonium chloride; allylamine such as allylamine benzoate and diallyldimethylammonium chloride; and derivatives thereof. be able to. The monomers exemplified above are only a part of copolymerizable monomers, and are exemplified in “Polyvinyl Chloride” edited by Kinki Chemical Association Vinyl Subcommittee, Nikkan Kogyo Shimbun (1988), pp. 75-104. Various monomers can be used. One or two or more of these comonomers can be copolymerized.
Further, a resin such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, vinyl chloride or a copolymerizable monomer described above with vinyl chloride. And resins obtained by graft polymerization of These vinyl chloride resins may be produced by any conventionally known production method such as suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization. The average degree of polymerization of the vinyl chloride resin is preferably from 600 to 3,000, more preferably from 800 to 1,500, as measured according to JIS K6721. If the average degree of polymerization of the vinyl chloride resin is less than 600, the mechanical properties of the obtained soft sheet may be reduced. If the average degree of polymerization of the vinyl chloride resin exceeds 3,000, kneading and molding become difficult, and it may be difficult to uniformly disperse the wood powder in the resin composition.
[0006]
In the composition of the present invention, as the component (B), chlorinated polyethylene is contained in an amount of 0.5 to 30 parts by weight, more preferably 3 to 15 parts by weight, per 100 parts by weight of the vinyl chloride resin. The chlorinated polyethylene used in the composition of the present invention is a non-crystalline polyethylene obtained by chlorinating a polyethylene resin having an ethylene content of 50% by weight or more, and preferably has a chlorine content of 20 to 50% by weight. More preferably, the amount is from 25 to 45% by weight. When the chlorine content is less than 20% by weight, the effect of improving the tensile elongation at break decreases. When the chlorine content exceeds 45% by weight, the periphery of the bank is deteriorated, and the roll kneading property is deteriorated. The Mooney viscosity (MS _{1 + 4} 100 ° C.) of the chlorinated polyethylene is preferably from 60 to 90, and more preferably from 65 to 85. If the Mooney viscosity is less than 60 or more than 90, the mixing of the vinyl chloride resin and the chlorinated polyethylene may be uneven. Chlorinated polyethylene has an effect of uniformly dispersing wood flour, reducing torque and improving moldability. In the composition of the present invention, if the content of the chlorinated polyethylene is less than 0.5 part by weight per 100 parts by weight of the vinyl chloride resin, there is a possibility that the periphery of the bank is deteriorated. When the content of the chlorinated polyethylene exceeds 30 parts by weight per 100 parts by weight of the vinyl chloride resin, the viscosity of the composition increases, and heat may be stored to impair the thermal stability of the flexible sheet.
[0007]
In the composition of the present invention, wood powder having an average particle size of 30 to 500 μm, more preferably 50 to 100 μm, is contained as the component (C). The content of the wood flour is 15 to 150 parts by weight, preferably 22 to 120 parts by weight, more preferably 25 to 100 parts by weight, per 100 parts by weight of the vinyl chloride resin. In the composition of the present invention, by blending the chlorinated polyethylene as the component (B), even if the wood flour is blended in an amount exceeding 15 parts by weight per 100 parts by weight of the vinyl chloride-based resin, the wood flour and the vinyl chloride-based Since it is well compatible with the resin and can be uniformly dispersed, a rich woody feeling can be exhibited.
The tree species of the wood flour used in the present invention is not particularly limited, and for example, coniferous or hardwood timber pieces such as cedar, hemlock and lauan, wood such as planing chips and sawdust can be used. In order to obtain wood flour used as the component (C) in the composition of the present invention from these woods, for example, the wood is made into a relatively round wood flour having an average particle size of 30 to 500 μm using a crusher. Is preferred.
In the composition of the present invention, wood powder having hard small particles adhered to the surface disclosed in JP-A-5-177610 and JP-A-5-261708 can be used as the wood powder. The mode in which the hard small particles adhere to the surface of the wood flour includes hard small particles such as an entanglement bond including biting of the hard small particles into the wood flour, and a pinch bond between a plurality of bite-bonded hard small particles. Adhesion to the wood flour surface may be performed by an external force, or hard small particles may be made to adhere to the wood flour using an adhesive. In this case, it is preferable that the wood flour is charged together with 1 to 50% by weight of hard small particles in a ball mill or the like and subjected to a treatment for preventing dust explosion such as placing it in a nitrogen atmosphere.
In the composition of the present invention, the average particle size of the wood flour refers to a reading of the value of the mesh corresponding to 50% by weight of the powder by classifying the powder with a sieve to form a cumulative weight% curve with respect to the mesh. When the average particle size of the wood flour is less than 30 μm, the bulk specific gravity becomes small, and the mixing operability for preparing the composition may be deteriorated. If the average particle size of the wood powder exceeds 500 μm, the surface of the soft sheet may be roughened, and the woody feeling may be reduced. If the content of the wood powder is less than 15 parts by weight per 100 parts by weight of the vinyl chloride resin, it may be difficult to give the soft sheet a sufficient woody feel. When the content of the wood powder exceeds 150 parts by weight per 100 parts by weight of the vinyl chloride resin, the mechanical strength of the soft sheet may be reduced. The water content of the wood flour is preferably 10% by weight or less, more preferably 5% by weight or less.
[0008]
In the composition of the present invention, as the component (D), a plasticizer is contained in an amount of 25 to 200 parts by weight, more preferably 40 to 120 parts by weight, per 100 parts by weight of the vinyl chloride resin. The plasticizer to be used is not particularly limited, and those conventionally used as plasticizers for vinyl chloride resin compositions, such as dibutyl phthalate, diisobutyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, Phthalate ester plasticizers such as dinonyl phthalate, diisodecyl phthalate and butylbenzyl phthalate; adipate ester plasticizers such as di-2-ethylhexyl adipate, diisononyl adipate and diisodecyl adipate; di-n-hexyl azelate, di- Azelaic acid ester plasticizers such as 2-ethylhexyl azelate and diisooctyl azelate; sebacic acid ester plasticizers such as di-n-butyl sebacate and di-2-ethylhexyl sebacate; di-n-butyl maleate; Jee Maleic ester plasticizers such as -ethylhexyl maleate; fumarate ester plasticizers such as di-n-butyl fumarate and di-2-ethylhexyl fumarate; tri-n-hexyl trimellitate, tri-2- Trimellitate plasticizers such as ethylhexyl trimellitate and tri-n-octyl trimellitate; pyromellitic ester plasticizers such as tetra-2-ethylhexyl pyromellitate and tetra-n-octyl pyromellitate; Citrate plasticizers such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-2-ethylhexyl citrate; diethyl itaconate, dibutyl itaconate, di-2-ethyl hexyl itaconate and the like Itaconic acid ester Plasticizers; other fatty acid ester plasticizers such as diethylene glycol diperargonate and various fatty acid esters of pentaerythritol; triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate Phosphate plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethylhexanoate, dibutyl methylene Glycol plasticizers such as bisthioglycolate; glycerol monoacetate, glycerol triacetate, glycerolt Glycerin-based plasticizers such as ribtylate; epoxidized soybean oil, epoxybutyl stearate, epoxy-2-diethylhexyl hexahexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxy triglyceride, octyl oleate epyl, epyl decyl oleate Epoxy plasticizers such as adipic acid polyester, sebacic polyester, and phthalic polyester, or partially hydrogenated terphenyl, adhesive plasticizers, and diallyl phthalate, acrylic monomers and oligomers And the like. In the present invention, among these, phthalate plasticizers can be particularly preferably used. One of these plasticizers can be used alone, or two or more can be used in combination.
When the content of the plasticizer in the composition of the present invention is less than 25 parts by weight per 100 parts by weight of the vinyl chloride resin, the sheet may be easily cut, and the production of a flexible sheet may be difficult. If the content of the plasticizer exceeds 200 parts by weight per 100 parts by weight of the vinyl chloride resin, the plasticizer may easily bleed from the surface of the soft sheet.
The composition of the present invention includes, in addition to the above-mentioned components, a heat stabilizer and a lubricant, which are blended in an ordinary vinyl chloride resin composition, an ultraviolet absorber, an impact resistance enhancer, a processing aid, and a charging agent. An inhibitor, a foaming agent, and the like can be appropriately added.
[0009]
In order to prepare the composition of the present invention, (A) a vinyl chloride resin, (B) chlorinated polyethylene, (C) wood flour, and (D) a plasticizer are generally put together in a mixer such as a Henschel mixer. Charge the mixture and raise the temperature to 120 to 160 ° C. with vigorous stirring and mixing. In this mixing process, the moisture absorbed in the wood flour is volatilized. By using a Henschel mixer or the like to charge all the components at once and mixing them, it is possible to obtain a mixture having a large bulk specific gravity and a uniformly dispersed additive such as a pigment. After reaching the above temperature, the mixture is transferred to a cooling mixer and cooled while further mixing. After the temperature of the mixture in the cooling mixer has sufficiently decreased, the mixture is removed from the cooling mixer in a powder state. The powdery mixture taken out can be used as it is as a molding compound or can be further pelletized. As a method of pelletizing, for example, using a single-screw extruder or twin-screw extruder with a vent, the cylinder temperature and the die temperature are set to 150 to 170 ° C, and the pellets are discharged while discharging the residual moisture in the wood flour through the vent hole. Can be mentioned.
There is no particular limitation on a molding method for obtaining a soft vinyl chloride resin sheet having a woody texture similar to natural wood using the composition of the present invention, and it can be usually molded by calendering or the like.
[0010]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In Examples and Comparative Examples, the area around the banks was evaluated according to the following criteria, and the tensile properties were tested according to the following methods.
(1) Around the bank A: The bite into the roll is good and can be kneaded stably.
B: Occasionally a state in which the roll does not bite occurs, and kneading becomes unstable.
C: It is difficult to bite into a roll, and stable kneading cannot be performed.
(2) Tensile test According to JIS K 7157, tensile strength, tensile elongation at break and 100% modulus were determined.
Example 1
100 parts by weight of vinyl chloride resin [ZEST1000Z, Shin Daiichi PVC Co., Ltd., average degree of polymerization 1050], chlorinated polyethylene [Eraslen 301A, Showa Denko KK, non-crystalline chlorinated polyethylene, chlorine content 30% by weight, Mooney viscosity 70 (MS _{1 + 4} 100 ° C) 5 parts by weight, wood flour [Selyunto, Shimada Shokai Co., Ltd., average particle size 80 µm, water content 5% by weight] 30 parts by weight, plasticizer [di-2-ethylhexyl phthalate] 65 Parts by weight, heat stabilizer [barium stearate / lead stearate composite heat stabilizer] 4 parts by weight, lubricant [n-butyl stearate] 0.5 part by weight, and filler [calcium carbonate, CCR, Shiraishi calcium Co., Ltd.] , An average particle size of 0.08 μm] was charged into a Henschel mixer, and water vapor was volatilized while mixing. And then, the mixture was further while cooling mixture transferred to a cooling mixer to obtain a powdery mixture.
The obtained powdery mixture was wound using an 8-inch roll set at a roll interval of 1 mm and a temperature of 150 ° C. for 1 minute, and kneaded with a knife for 5 minutes. The bite of the bank was good, and the kneading could be performed stably. After kneading, a soft sheet having a thickness of 1 mm was obtained. The obtained soft sheet had a rich woody feeling. A tensile test was performed on the obtained soft sheet. The tensile strength was 1.19 kgf / cm ² , the tensile elongation at break was 300%, and the 100% modulus was 0.65 kgf / cm ² .
Examples 2-3
For the composition having the composition shown in Table 1, the bite of the bank was evaluated using an 8-inch roll in the same manner as in Example 1, and a soft sheet having a thickness of 1 mm was further prepared. Elongation and 100% modulus were measured. The results are shown in Table 1.
Comparative Examples 1-3
For the composition having the composition shown in Table 1, the bite of the bank was evaluated using an 8-inch roll in the same manner as in Example 1, and a soft sheet having a thickness of 1 mm was further prepared. Elongation and 100% modulus were measured. The results are shown in Table 1.
[0011]
[Table 1]

[0012]
[note]
1) ZEST1000Z, Shin Daiichi PVC Co., Ltd., average degree of polymerization 1050.
2) Eraslen 301A, Showa Denko KK, amorphous chlorinated polyethylene, chlorine content 30% by weight, Mooney viscosity 70 (MS _{1 + 4} 100 ° C).
3) Hybrene B403, Nippon Zeon Co., Ltd., a copolymer having about 90% by weight of methyl methacrylate units, specific viscosity 2.06 (0.2 g / dl chloroform solution, measured at 25 ° C.).
4) Cellyunto, Shimada Shokai Co., Ltd., average particle size 80 μm, water content 5% by weight.
5) E60-T5-3, Misawa Techno Co., Ltd., wood powder adhered with titanium oxide particles, titanium oxide content 5% by weight, average particle size 60 μm, water content 5% by weight.
6) di-2-ethylhexyl phthalate.
7) Barium stearate / zinc stearate heat stabilizer.
8) n-butyl stearate.
9) Calcium carbonate, CCR, manufactured by Shiraishi Calcium Co., Ltd., average particle size 0.08 μm.
From the results in Table 1, the vinyl chloride resin compositions of Examples 1 to 3 of the present invention containing chlorinated polyethylene have good bite into the roll of the bank and can be stably kneaded, It can be seen that the resulting sheet has a suitable tensile elongation at break and a 100% modulus as a soft sheet.
On the other hand, the vinyl chloride resin composition of Comparative Example 1 containing no chlorinated polyethylene has a poor bite into the roll of the bank. In place of the chlorinated polyethylene of Example 1, the vinyl chloride resin composition of Comparative Example 2 in which a methacrylic acid ester resin as a processing aid was added, the bite of the bank into the roll was poor, and Even when the content of the methacrylic acid ester-based resin is increased as in Comparative Example 3, the periphery of the bank is not so much improved.
[0013]
【The invention's effect】
The vinyl chloride resin-based composition of the present invention has a good bite into a roll of a bank, can be kneaded and formed into a sheet stably, and can obtain a soft sheet suitable for an interior material with a rich woody feel. it can.

Claims (1)

(A) 100 parts by weight of vinyl chloride resin, (B) 0.5 to 30 parts by weight of chlorinated polyethylene, (C) 15 to 150 parts by weight of wood powder having an average particle size of 50 to 500 μm, and (D) plasticizer 25 to A vinyl chloride resin composition containing 200 parts by weight.