KR20170008175A - Pvc composition, as well as electric wire and cable using the same - Google Patents
Pvc composition, as well as electric wire and cable using the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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Abstract
(과제)
본 발명은, 가소제로서 테레프탈산 에스테르를 사용하여도 내후성 및 내블리드성이 양호한 염화비닐수지 조성물, 및 이것을 사용한 전선 및 케이블을 제공하는 것이다.
(해결수단)
전선(10)은, 도체(1)의 외주에, 가소제로서 테레프탈산 에스테르를 함유하며 염화비닐수지 100질량부에 대하여 상기 테레프탈산 에스테르를 100질량부 이하, 실리콘오일을 0.1질량부 이상, 아디핀산 에스테르를 1질량부 이상 함유하는 염화비닐수지 조성물로 이루어지는 절연층(2)을 구비한다.(assignment)
The present invention provides a vinyl chloride resin composition having excellent weather resistance and bleeding resistance even when terephthalic acid ester is used as a plasticizer, and to provide electric wires and cables using the same.
(Solution)
The electric wire (10) contains terephthalic acid ester as a plasticizer on the outer periphery of the conductor (1) and contains not more than 100 parts by mass of the terephthalic acid ester, not less than 0.1 part by mass of a silicone oil, And an insulating layer (2) made of a vinyl chloride resin composition containing not less than 1 part by mass.
Description
본 발명은, 염화비닐수지 조성물, 및 이것을 사용한 전선 및 케이블에 관한 것이다.
BACKGROUND OF THE
염화비닐수지(PVC)는, 저비용이며 난연성(難燃性)을 구비하는 재료로, 유연성(柔軟性)을 부여하기 위한 가소제(可塑劑)를 첨가함으로써 전선피복재(電線被覆材)로서 사용된다.BACKGROUND ART PVC is a low cost flame retardant material and is used as a wire covering material by adding a plasticizer for imparting flexibility.
가소제로서는, 저렴하고 PVC와의 상용성(相溶性)이 높은 디-2-에틸헥실프탈레이트(DOP)가 주로 사용되지만(예를 들면 특허문헌1 참조), 근년 REACH 규정과 더불어 RoHS 지령의 사용금지물질로 지정될 우려도 있어, 이후의 사용이 꺼려지고 있다.As the plasticizer, di-2-ethylhexyl phthalate (DOP), which is inexpensive and highly compatible with PVC, is mainly used (see, for example, Patent Document 1). However, in recent years, There is a concern that it may be designated as "
DOP의 대체후보로서는, DOP 다음으로 전선피복재로서 사용실적이 있는 디이소노닐프탈레이트(DINP)를 들 수 있지만(예를 들면 특허문헌2 참조), DINP는 고무 용도로도 사용되어 공급부족을 일으킬 가능성이 있기 때문에, 그 외의 가소제의 실용화가 요구되고 있다.As a substitute candidate for DOP, diisononyl phthalate (DINP) which has been used as a wire covering material after DOP can be mentioned (see, for example, Patent Document 2), but DINP is also used for rubber, There is a demand for practical use of other plasticizers.
그 외의 가소제로서는, DOP, DINP와 동등한 PVC와의 상용성을 구비하는 테레프탈산 에스테르 구조의 가소제가 있다(예를 들면 특허문헌3∼4 참조). 의료용 기구에 사용되는 것으로서는, 디(2-에틸헥실)테레프탈레이트가 배합된 염화비닐수지 조성물이 특허문헌5에 기재되어 있다.
As other plasticizers, there are plasticizers of a terephthalic acid ester structure having compatibility with PVC equivalent to DOP and DINP (see, for example,
그러나 하기 일반식(1)로 나타내는 테레프탈산 에스테르는, 하기 일반식(2)로 나타내는 프탈산 에스테르와 비교하여 내후성(耐候性)이 떨어지기 때문에, 전선 용도로 옥외에서 사용하는 데에는 문제가 있다(각 식 중의 R은 알킬쇄를 나타낸다).However, the terephthalic acid ester represented by the following general formula (1) has a problem in that it is used outdoors for electric wires because the weather resistance is lower than that of the phthalic acid ester represented by the following general formula (2) Lt; / RTI > represents an alkyl chain.
(화학식1)(Formula 1)
(화학식2)(2)
또한 첨가제 중에는, PVC나 테레프탈산 에스테르와 상용(相溶)되기 어려워, 조성물의 표면에 블리드(bleed)하여 끈적임을 발생시키는 문제가 있는 것이 있다.In addition, some of the additives are difficult to be compatible with PVC or terephthalic acid ester, and there is a problem that bleeding occurs on the surface of the composition to cause tackiness.
그래서 본 발명은, 가소제로서 테레프탈산 에스테르를 사용하여도 내후성 및 내블리드성이 양호한 염화비닐수지 조성물, 및 이것을 사용한 전선 및 케이블을 제공하는 것을 목적으로 한다.
Therefore, it is an object of the present invention to provide a vinyl chloride resin composition having excellent weather resistance and bleeding resistance even when terephthalic acid ester is used as a plasticizer, and to provide electric wires and cables using the composition.
상기 목적을 달성하기 위한 본 발명에 의하면, 이하의 염화비닐수지 조성물, 및 이것을 사용한 전선 및 케이블이 제공된다.In order to accomplish the above object, the present invention provides the following vinyl chloride resin composition, and wires and cables using the same.
[1] 가소제로서 테레프탈산 에스테르를 함유하는 염화비닐수지 조성물에 있어서, 염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 100질량부 이하, 실리콘오일을 0.1질량부 이상, 아디핀산 에스테르를 1질량부 이상 함유하는 염화비닐수지 조성물.[1] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein 100 parts by mass or less of the terephthalic acid ester, 0.1 parts by mass or more of the silicone oil and 1 part by mass of the adipic acid ester are contained per 100 parts by mass of the vinyl chloride resin By weight based on the total weight of the composition.
[2] 염화비닐수지 100질량부에 대하여, 상기 실리콘오일을 0.1∼2.5질량부, 아디핀산 에스테르를 1∼30질량부 함유하는 상기 [1]에 기재되어 있는 염화비닐수지 조성물.[2] The vinyl chloride resin composition according to the above [1], which contains 0.1 to 2.5 parts by mass of the silicone oil and 1 to 30 parts by mass of adipic acid ester per 100 parts by mass of the vinyl chloride resin.
[3] 염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 10∼100질량부 함유하는 상기 [1] 또는 상기 [2]에 기재되어 있는 염화비닐수지 조성물.[3] The vinyl chloride resin composition according to [1] or [2], wherein the vinyl chloride resin contains 10 to 100 parts by mass of the terephthalic acid ester per 100 parts by mass of the vinyl chloride resin.
[4] 상기 테레프탈산 에스테르는, 1개당 알킬쇄의 탄소수가 8∼10인 테레프탈산 에스테르인 상기 [1] 내지 [3] 중의 어느 하나에 기재되어 있는 염화비닐수지 조성물.[4] The vinyl chloride resin composition according to any one of [1] to [3], wherein the terephthalic acid ester is a terephthalic acid ester having an alkyl chain of 8 to 10 carbon atoms per one ester.
[5] 상기 아디핀산 에스테르는, 1개당 알킬쇄의 탄소수가 8∼10인 아디핀산 에스테르인 상기 [1] 내지 [4] 중의 어느 하나에 기재되어 있는 염화비닐수지 조성물.[5] The vinyl chloride resin composition according to any one of [1] to [4], wherein the adipic acid ester is an adipic acid ester having an alkyl chain of 8 to 10 carbon atoms per one unit.
[6] 가소제로서 테레프탈산 에스테르를 함유하는 염화비닐수지 조성물에 있어서, 염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 100질량부 이하, 실리콘오일을 0.1질량부 이상, 아디핀산 에스테르를 1질량부 이상 함유하는 염화비닐수지 조성물로 이루어지는 절연층을 구비한 전선.[6] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer is characterized by containing 100 parts by mass or less of the terephthalic acid ester, 0.1 parts by mass or more of the silicone oil and 1 part by mass of the adipic acid ester per 100 parts by mass of the vinyl chloride resin Or more of the vinyl chloride resin composition.
[7] 가소제로서 테레프탈산 에스테르를 함유하는 염화비닐수지 조성물에 있어서, 염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 100질량부 이하, 실리콘오일을 0.1질량부 이상, 아디핀산 에스테르를 1질량부 이상 함유하는 염화비닐수지 조성물로 이루어지는 시스를 구비한 케이블.[7] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein 100 parts by mass or less of the terephthalic acid ester, 0.1 parts by mass or more of the silicone oil, 1 part by mass of the adipic acid ester Or more of a vinyl chloride resin composition.
[8] 상기 [6]에 기재되어 있는 전선을 구비한 상기 [7]에 기재되어 있는 케이블.
[8] A cable according to the above-mentioned [7], which has the electric wire described in [6] above.
본 발명에 의하면, 가소제로서 테레프탈산 에스테르를 사용하여도 내후성 및 내블리드성이 양호한 염화비닐수지 조성물, 및 이것을 사용한 전선 및 케이블이 제공된다.
INDUSTRIAL APPLICABILITY According to the present invention, a vinyl chloride resin composition having excellent weather resistance and bleeding resistance even when terephthalic acid ester is used as a plasticizer, and electric wires and cables using the same are provided.
도1은, 본 발명의 실시형태에 관한 전선의 일례를 모식적으로 나타내는 횡단면도이다.
도2는, 본 발명의 실시형태에 관한 케이블의 일례를 모식적으로 나타내는 횡단면도이다.1 is a cross-sectional view schematically showing an example of electric wires according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing an example of a cable according to an embodiment of the present invention.
〔염화비닐수지 조성물〕[Vinyl chloride resin composition]
본 발명의 실시형태에 관한 염화비닐수지 조성물은, 가소제로서 테레프탈산 에스테르를 함유하는 염화비닐수지 조성물로서, 염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 100질량부 이하, 실리콘오일을 0.1질량부 이상, 아디핀산 에스테르를 1질량부 이상 함유한다.A vinyl chloride resin composition according to an embodiment of the present invention is a vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer. The vinyl chloride resin composition contains 100 parts by mass or less of the terephthalic acid ester, 0.1 parts by mass Or more and 1 part by mass or more of adipic acid ester.
본 발명자는, 테레프탈산 에스테르가 내후성이 떨어지는 이유로는, 테레프탈산 에스테르는 에스테르의 카르복실기가 열린 구조여서, 외부로부터 침투되는 물과의 접촉이 용이하게 되어 가수분해성이 높기 때문이라고 생각했다.The inventor of the present invention believed that the reason why the terephthalic acid ester is poor in weatherability is that the terephthalic acid ester has a structure in which the carboxyl group of the ester is opened so that the terephthalic acid ester is easily contacted with the water permeated from the outside and has high hydrolysis ability.
그래서 테레프탈산 에스테르를 사용할 때의 내후성의 열화를 억제하기 위하여, 다양한 첨가제에 대하여 첨가를 검토한 결과, 발수성(撥水性)이 뛰어난 실리콘오일을 첨가함으로써 내후성을 개선할 수 있다는 것을 발견하였다.Therefore, in order to suppress deterioration of weatherability when using terephthalic acid ester, various additives have been added. As a result, it has been found that the addition of a silicone oil excellent in water repellency can improve weather resistance.
그러나 실리콘오일은, PVC나 테레프탈산 에스테르와 상용되기 어려워, 조성물의 표면에 블리드하여 끈적임을 발생시키는 문제가 있었다.However, the silicone oil is difficult to be compatible with PVC or terephthalic acid ester, and has a problem of causing stickiness by bleeding on the surface of the composition.
그래서 테레프탈산 에스테르와 실리콘오일 쌍방과 상용되기 쉽고 PVC와도 상용될 수 있는 아디핀산 에스테르를 첨가함으로써, 내후성과 내블리드성을 양립시킨 본 발명의 염화비닐수지 조성물을 개발할 수 있었다.Thus, by adding an adipic acid ester, which is easily compatible with both terephthalic acid ester and silicone oil and can also be used with PVC, it is possible to develop the vinyl chloride resin composition of the present invention which has both weather resistance and bleeding resistance.
(테레프탈산 에스테르)(Terephthalic acid ester)
본 발명의 실시형태에 관한 염화비닐수지 조성물에서 가소제로서 사용되는 테레프탈산 에스테르로는, 1개당 알킬쇄의 탄소수가 8∼10(C8∼C10)인 테레프탈산 에스테르가 적합하다. C8 미만으로는 필요한 내열성(耐熱性)을 얻기 어렵다. 알킬쇄의 탄소수가 적을수록, 즉 분자량이 작을수록 가열에 의한 가소제의 휘발이 촉진되어, 염화비닐수지 조성물이 경화되기 때문이다. 한편 C11 이상이면, 가소제의 에스테르 합성에 필요한 알코올의 입수가 곤란하여 비용이 늘어나기 때문에 실용성이 떨어져, C10 이하인 것이 바람직하다.As the terephthalic acid ester used as the plasticizer in the vinyl chloride resin composition according to the embodiment of the present invention, a terephthalic acid ester having an alkyl chain of 8 to 10 carbon atoms (C8 to C10) per one is preferable. If it is less than C8, it is difficult to obtain necessary heat resistance (heat resistance). The smaller the number of carbon atoms in the alkyl chain, that is, the smaller the molecular weight, the more the volatilization of the plasticizer due to heating promotes the curing of the vinyl chloride resin composition. On the other hand, if C11 or more, it is difficult to obtain an alcohol necessary for synthesizing an ester of a plasticizer, and the cost is increased, so practicality deteriorates, and C10 or less is preferable.
테레프탈산 에스테르의 알킬쇄는, 직쇄 구조(直鎖 構造)이어도 분기쇄 구조(分岐鎖 構造)이어도 좋지만, 분기쇄 구조인 것이 바람직하다. 구체적으로는, C8인 것으로서 디-2-에틸헥실테레프탈레이트(DOTP), C9인 것으로서 디이소노닐테레프탈레이트(DINTP), C10인 것으로서 디이소데실테레프탈레이트(DIDTP)를 들 수 있지만, 이들에 한정되는 것은 아니다.The alkyl chain of the terephthalic ester may be a straight chain structure (straight chain structure) or a branched chain structure (branched chain structure), but it is preferably a branched chain structure. Specifically, C8 is di-2-ethylhexyl terephthalate (DOTP), C9 is diisononyl terephthalate (DINTP), and C10 is diisodecyl terephthalate (DIDTP) It is not.
본 발명의 실시형태에 있어서 상기 테레프탈산 에스테르의 첨가량은, 염화비닐수지 100질량부에 대하여 100질량부 이하로 한다. 10질량부 이상 첨가하는 것이 바람직하다. 실리콘오일을 첨가함으로써 테레프탈산 에스테르의 첨가에 대한 효과가 발휘되지만, 테레프탈산 에스테르의 첨가량이 100질량부를 넘으면, 가소제 자체가 블리드하여 표면에 끈적임이 발생한다.In the embodiment of the present invention, the amount of the terephthalic acid ester added is 100 parts by mass or less based on 100 parts by mass of the vinyl chloride resin. 10 parts by mass or more is preferably added. When the addition amount of the terephthalic acid ester is more than 100 parts by mass, the plasticizer itself is bleached and sticky to the surface occurs.
(실리콘오일)(Silicone oil)
본 발명의 실시형태에 관한 염화비닐수지 조성물에 사용되는 실리콘오일로서는, 예를 들면 디메틸 실리콘오일, 메틸하이드로겐 실리콘오일, 메틸페닐 실리콘오일이 적합하다. 스트레이트 실리콘오일에 한정되지 않고, 변성 실리콘오일이더라도 좋다.As the silicone oil used in the vinyl chloride resin composition according to the embodiment of the present invention, for example, dimethylsilicone oil, methylhydrogen silicone oil and methylphenyl silicone oil are suitable. The modified silicone oil is not limited to the straight silicone oil.
본 발명의 실시형태에 있어서 상기 실리콘오일의 첨가량은, 염화비닐수지 100질량부에 대하여 0.1질량부 이상이 필요하다. 첨가량 0.1질량부 미만으로는 필요한 내후성을 얻을 수 없다. 또한 첨가량은 2.5질량부 이하인 것이 바람직하다. 2.5질량부를 넘으면, 가공성에 문제가 생기기 쉽다.In the embodiment of the present invention, the addition amount of the silicone oil is 0.1 part by mass or more based on 100 parts by mass of the vinyl chloride resin. When the addition amount is less than 0.1 part by mass, required weather resistance can not be obtained. The addition amount is preferably 2.5 parts by mass or less. If the amount exceeds 2.5 parts by mass, the workability tends to be problematic.
(아디핀산 에스테르)(Adipic acid ester)
본 발명의 실시형태에 관한 염화비닐수지 조성물에 사용되는 아디핀산 에스테르로서는, 1개당 알킬쇄의 탄소수가 8∼10(C8∼C10)인 아디핀산 에스테르가 적합하다.As the adipic acid ester used in the vinyl chloride resin composition according to the embodiment of the present invention, an adipic acid ester having an alkyl chain of 8 to 10 carbon atoms (C8 to C10) per one is suitable.
아디핀산 에스테르의 알킬쇄는, 직쇄 구조이어도 분기쇄 구조이어도 좋지만, 분기쇄 구조인 것이 바람직하다. 구체적으로는, C8인 것으로서 디-2-에틸헥실아디페이트(DOA), C9인 것으로서 디이소노닐아디페이트(DINA), C10인 것으로서 디이소데실아디페이트(DIDA)를 들 수 있지만, 이들에 한정되는 것은 아니다.The alkyl chain of the adipic ester may be either straight chain structure or branched chain structure, but is preferably branched chain structure. Specifically, C8 is di-2-ethylhexyl adipate (DOA), C9 is diisononyl adipate (DINA), and C10 is diisodecyl adipate (DIDA) It is not.
본 발명의 실시형태에 있어서 상기 아디핀산 에스테르의 첨가량은, 염화비닐수지 100질량부에 대하여 1질량부 이상이 필요하다. 첨가량 1질량부 미만으로는 실리콘오일의 블리드를 억제할 수 없다. 또한 첨가량은 30질량부 이하인 것이 바람직하다. 30질량부를 넘으면, 가공성에 문제가 생기기 쉽다.In the embodiment of the present invention, the addition amount of the adipic acid ester is 1 part by mass or more based on 100 parts by mass of the vinyl chloride resin. If the addition amount is less than 1 part by mass, the bleeding of the silicone oil can not be suppressed. The addition amount is preferably 30 parts by mass or less. If the amount exceeds 30 parts by mass, the workability tends to be problematic.
(염화비닐수지)(Vinyl chloride resin)
염화비닐수지로서는, 염화비닐의 단독 중합체(즉, 폴리염화비닐) 외에, 염화비닐과 공중합 가능한 다른 모노머와의 공중합체 및 이들의 혼합물을 들 수 있다. 염화비닐과 공중합 가능한 모노머로서는, 아세트산비닐, 염화비닐리덴, (메타)아크릴산, 아크릴로니트릴 등을 들 수 있다.Examples of the vinyl chloride resin include a homopolymer of vinyl chloride (that is, polyvinyl chloride), a copolymer of vinyl chloride and other monomers copolymerizable with vinyl chloride, and mixtures thereof. Examples of the monomer copolymerizable with vinyl chloride include vinyl acetate, vinylidene chloride, (meth) acrylic acid, acrylonitrile and the like.
염화비닐수지는, 평균중합도가 1000∼2500인 것을 사용하는 것이 바람직하다. 평균중합도가 1000∼2000인 것이 내열성, 내한성(耐寒性), 성형성(成形性)의 면에서 더 바람직하다. 중합도가 낮아지면 성형성은 향상되지만 내열성, 내한성이 저하된다. 반대로 중합도가 높아지면 내열성, 내한성은 향상되지만 성형성이 나빠진다.The vinyl chloride resin preferably has an average degree of polymerization of 1000 to 2500. It is more preferable that the average degree of polymerization is 1000 to 2000 in terms of heat resistance, cold resistance and moldability. If the degree of polymerization is lowered, the moldability is improved but the heat resistance and cold resistance are lowered. On the contrary, if the polymerization degree is increased, the heat resistance and cold resistance are improved but the moldability is deteriorated.
염화비닐수지는, 필요에 따라 중합도가 다른 것을 2종류 이상 블렌드(blend)하여 사용하여도 좋다.The vinyl chloride resin may be blended with two or more kinds of resins having different degrees of polymerization, if necessary.
(그 외의 성분)(Other components)
본 발명의 실시형태에 있어서는, 본 발명의 효과를 얻을 수 있는 한, 상기 성분 이외에, PVC 이외의 폴리머, 무기충전제, 안정제, 산화방지제, 가소제, 활제(滑劑), 착색제, 자외선흡수제, 광안정제, 가교제, 가교조제 등의 첨가제를 다양하게 배합할 수 있다.In the embodiments of the present invention, as long as the effect of the present invention can be obtained, in addition to the above components, a polymer other than PVC, an inorganic filler, a stabilizer, an antioxidant, a plasticizer, a lubricant, a colorant, , Cross-linking agent, cross-linking assistant, and the like.
예를 들면 내열성·내한성·절연성 등을 향상시키고자 하는 경우에는, 필요에 따라 프탈산 에스테르, 이소프탈산 에스테르, 트리멜리트산 에스테르, 피로멜리트산 에스테르, 에폭시화 대두유 등의 다른 가소제를 블렌드하여 사용하여도 좋다.For example, when it is desired to improve the heat resistance, cold resistance, insulation and the like, other plasticizers such as phthalic acid ester, isophthalic acid ester, trimellitic acid ester, pyromellitic acid ester and epoxidized soybean oil may be blended good.
〔전선〕〔wire〕
본 발명의 실시형태에 관한 전선은, 도체(導體)와, 도체의 외주(外周)에 피복(被覆)되며 본 발명의 실시형태에 관한 상기 염화비닐수지 조성물로 이루어지는 절연층(絶緣層)을 구비하는 것을 특징으로 한다.The electric wire according to the embodiment of the present invention includes a conductor and an insulating layer formed of the vinyl chloride resin composition according to the embodiment of the present invention coated on the outer circumference of the conductor .
도1은, 본 발명의 실시형태에 관한 전선의 일례를 모식적으로 나타내는 횡단면도이다.1 is a cross-sectional view schematically showing an example of electric wires according to an embodiment of the present invention.
도1에 나타나 있는 바와 같이 본 실시형태에 관한 전선(10)은, 도체(1)와, 도체(1)의 외주에 피복된 절연층(2)을 구비한다. 피복되는 도체(1)로서는, 예를 들면 외경이 0.15∼7mmφ 정도인 도체를 사용할 수 있다. 주석도금 연동선(tin-plated 軟銅線)을 꼬아 만든 도체 등을 적합하게 사용할 수 있지만, 이에 한정되는 것은 아니다. 도체(1)는, 도1과 같이 1개인 경우로 한정되지 않고 복수 개이더라도 좋다.As shown in Fig. 1, the
절연층(2)은, 본 발명의 실시형태에 관한 상기의 염화비닐수지 조성물로 구성되어 있다. 압출피복(壓出被覆) 등의 성형수단에 의하여 절연층으로서 피복함으로써 전선(10)을 얻을 수 있다. 필요에 따라 전자선 조사 등의 방법에 의하여 가교처리를 하여도 좋다.The insulating
본 실시형태에 있어서는, 도1에서와 같이 절연층을 단층으로 구성하였지만, 다층구조로 하는 것도 가능하다. 이 경우에 적어도 최외층(最外層)은, 상기 염화비닐수지 조성물을 사용하여 형성한다.In this embodiment, the insulating layer is formed of a single layer as shown in Fig. 1, but it may be a multi-layered structure. In this case, at least the outermost layer (outermost layer) is formed using the vinyl chloride resin composition.
〔케이블〕〔cable〕
본 발명의 실시형태에 관한 케이블은, 본 발명의 실시형태에 관한 상기 염화비닐수지 조성물을 피복재료(시스(sheath), 또는 절연층 및 시스)로서 사용하는 것을 특징으로 한다.The cable according to the embodiment of the present invention is characterized in that the vinyl chloride resin composition according to the embodiment of the present invention is used as a covering material (sheath, insulating layer and sheath).
도2는, 본 발명의 실시형태에 관한 케이블의 일례를 모식적으로 나타내는 횡단면도이다.2 is a cross-sectional view schematically showing an example of a cable according to an embodiment of the present invention.
도2에 나타나 있는 바와 같이 본 실시형태에 관한 케이블(20)은, 도체(1)에 절연층(2)을 피복한 상기 본 발명의 실시형태에 관한 전선(10) 3개를 종이 등의 개재물(介在物)(3)과 함께 꼬아 만든 3심 연선(三芯 撚線)과, 그 외주에 감긴 가압 테이프(4)와, 그 외주에 압출피복된 시스(5)를 구비한다. 3심 연선에 한하지 않고, 전선 1개(단심)로 하여도 좋고, 3심 이외의 다심 연선으로 하여도 좋다. 가압 테이프(4)는 생략할 수도 있고, 편조(編組)로 바꾸어도 좋다.2, the
시스(5)는, 본 발명의 실시형태에 관한 상기의 염화비닐수지 조성물로 구성되어 있다. 본 실시형태에 있어서는 절연층(2)도, 상기의 염화비닐수지 조성물로 구성하였지만, 이것에 한정되는 것은 아니고, 그 외의 절연층용 수지 조성물(논할로겐 난연성 수지 조성물인 것이 바람직하다)로 구성되어 있어도 좋다. 시스(5)는, 필요에 따라 전자선 조사 등의 방법에 의하여 가교처리를 하여도 좋다.The
본 실시형태에 있어서는, 도2에서와 같이 시스를 단층으로 구성하였지만, 다층구조로 하는 것도 가능하다. 이 경우에 적어도 최외층은, 상기 염화비닐수지 조성물을 사용하여 형성한다.In the present embodiment, the sheath is formed as a single layer as shown in Fig. 2, but a multi-layer structure can also be used. In this case, at least the outermost layer is formed by using the vinyl chloride resin composition.
(실시예)(Example)
이하에, 본 발명을 실시예에 의하여 더 구체적으로 설명한다. 또한 본 발명은, 이하의 실시예에 의하여 어떠한 제한을 받는 것이 아니다.Hereinafter, the present invention will be described more specifically by way of examples. The present invention is not limited by the following examples.
표1∼2에 실시예, 표3에 종래예 및 비교예를 나타낸다.Tables 1 and 2 show examples, and Table 3 shows conventional examples and comparative examples.
〈시험편(시트)의 제작방법〉≪ Method of producing test piece (sheet)
평균중합도가 1300인 PVC 100질량부에 대하여, 표1∼3에 나타낸 비율로 가소제, 실리콘오일, 안정제로서 칼슘-아연계 무연 안정제, 충전제로서 탄산칼슘을 혼합하였다. 그 후에 혼련(混練)(롤 온도 160℃, 5분)과 프레스(프레스 온도 180℃, 예열 3분, 가압 10MPa로 2분)에 의하여 두께가 1mm인 시트를 성형하였다. 또한 가소제는 롤로 혼련이 가능한 양으로서 40질량부 이상의 첨가가 필요하기 때문에, 테레프탈산 에스테르의 첨가량이 10질량부인 예에 있어서는 DINP(디이소노닐프탈레이트) 30질량부를 블렌드하여 제작하였다.Silicone oil, a calcium-zinc based lead-free stabilizer as a stabilizer and calcium carbonate as a filler were mixed in 100 parts by mass of PVC having an average degree of polymerization of 1300 in the ratios shown in Tables 1 to 3. Thereafter, a sheet having a thickness of 1 mm was formed by kneading (roll temperature 160 DEG C for 5 minutes) and a press (press temperature 180 DEG C, preheating 3 minutes,
표1∼3 중의 재료는 이하의 것을 사용하였다.The materials shown in Tables 1 to 3 were as follows.
(1) 염화비닐수지(신에쓰 가가쿠 고교 가부시키가이샤(Shin-Etsu Chemical Co., Ltd.) 제품, 상품명 : TK-1300)(1) A vinyl chloride resin (trade name: TK-1300, manufactured by Shin-Etsu Chemical Co., Ltd.)
(2) 가소제(2) a plasticizer
· 테레프탈산 에스테르· Terephthalic acid ester
DOTP(디-2-에틸헥실테레프탈레이트)DOTP (di-2-ethylhexyl terephthalate)
DINTP(디이소노닐테레프탈레이트)DINTP (diisononyl terephthalate)
DIDTP(디이소데실테레프탈레이트)DIDTP (diisodecyl terephthalate)
· 프탈산 에스테르Phthalic acid ester
DINP(디이소노닐프탈레이트)DINP (diisononyl phthalate)
DOP(디-2-에틸헥실프탈레이트)DOP (di-2-ethylhexyl phthalate)
· 아디핀산 에스테르Adipinic ester
DOA(디-2-에틸헥실아디페이트)DOA (di-2-ethylhexyl adipate)
DINA(디이소노닐아디페이트)DINA (diisononyl adipate)
DIDA(디이소데실아디페이트)DIDA (diisodecyl adipate)
(3) 실리콘오일(신에쓰 실리콘(Shin-Etsu Silicone) 제품, 상품명 : KF-96-100cs)(3) Silicone oil (product of Shin-Etsu Silicone, trade name: KF-96-100cs)
(4) 안정제 : Ca-Zn계 무연 안정제(4) Stabilizer: Ca-Zn based lead-free stabilizer
(5) 충전제 : 탄산칼슘(가부시키가이샤 마루토(Marutou CO., LTD) 제품, 상품명 : 소프톤1500(Softon1500))(5) Filler: Calcium carbonate (product of Marutou CO., LTD., Trade name: Softon 1500)
〈시험방법〉<Test Methods>
내후성은, 스가 시켄키 가부시키가이샤(Suga Test Instruments Co., Ltd.) 제품인 메탈할라이드 램프 내후촉진시험기(M6T)에 의하여 평가하였다. 시료면 방사조도 1.5kw/m2, 온도 60℃, 습도 50％, 광원-시료 간 거리 350mm, 조사시간 72시간(3분 수분무(水噴霧)＋117분 조사의 120분 사이클×36회)의 조건으로 조사하고, 조사 후/조사 전의 인장시험의 신장잔율(retention of elongation)과 조사 후의 외관을 평가하였다. 인장시험은 JISK 6723에 준거하여 하였다. 신장잔율의 평가판정은, 60％ 이상을 합격(○), 60％ 미만을 불합격(×)으로 하였다. 또한 외관의 평가판정은, 조사 후의 시료표면에 크랙(균열)이 없는 경우를 합격(○), 있는 경우를 불합격(×)으로 하였다. 내후성판정은, 신장잔율이 합격이고 또 외관이 합격인 경우를 합격(○)으로 하고, 어느 하나가 불합격인 경우에는 불합격(×)으로 하였다. 결과를 표1∼3에 나타낸다.The weather resistance was evaluated by a metal halide lamp weather resistance accelerator (M6T) manufactured by Suga Test Instruments Co., Ltd. The sample was irradiated with a radiation intensity of 1.5 kw / m 2 , a temperature of 60 ° C., a humidity of 50%, a distance between the light source and the sample of 350 mm, an irradiation time of 72 hours (120 minutes cycle × 36 times of 3 minutes water spraying + 117 minutes irradiation) , And the retention of elongation and the appearance after irradiation of the tensile test before and after irradiation were evaluated. The tensile test was carried out in accordance with JISK 6723. In the evaluation of the renal residual rate, 60% or more was judged as acceptable (O), and less than 60% was judged as rejection (X). In the evaluation of the external appearance evaluation, the case where there is no crack (crack) on the surface of the sample after irradiation is regarded as passing (?), And the case where it is rejected (x). In the weatherability test, the case where the elongation percentage is acceptable and the appearance is acceptable is regarded as pass (O), and in the case where any one of them is rejected, the rejection (X) is determined. The results are shown in Tables 1 to 3.
내블리드성은, 온도 70℃×습도 90％의 항온항습조(恒溫恒濕槽)에 의하여 평가하였다. 72시간 방치하고 취출한 후에, 표면에 끈적임이 없는 경우를 합격(○)으로 하고, 있는 경우를 불합격(×)으로 하였다. 결과를 표1∼3에 나타낸다.The bleed resistance was evaluated by a constant temperature and humidity chamber (temperature: 70 캜, humidity: 90%). After leaving for 72 hours and taking out, the case where there is no tackiness on the surface is regarded as passing (?), And the case where it is judged as not passing (占). The results are shown in Tables 1 to 3.
(표1)(Table 1)
실시예(배합량의 단위는 질량부)Example (Unit of the blending amount is in parts by mass)
(표2)(Table 2)
실시예(배합량의 단위는 질량부)Example (Unit of the blending amount is in parts by mass)
(표3)(Table 3)
종래예 및 비교예(배합량의 단위는 질량부)Conventional example and comparative example (the unit of the blending amount is mass part)
참고로 실시하였던 DOP 또는 DINP를 사용한 종래예1, 2에서는, 내후성·내블리드성 모두 합격이었다.In the prior art examples 1 and 2 using the DOP or DINP which were carried out for reference, both the weatherability and the bleeding resistance were acceptable.
실시예1 및 비교예1은 DOTP를 10질량부 첨가한 경우로서, 실리콘오일을 0.1질량부 및 DIDA를 1질량부 첨가한 실시예1에서는 내후성·내블리드성 모두 합격이었지만, 실리콘오일 및 DIDA를 첨가하지 않은 비교예1에서는 내후성시험 후에 크랙이 발생하여 외관이 불합격이었기 때문에, 내후성의 판정은 불합격이었다.In Example 1 and Comparative Example 1, 10 parts by mass of DOTP was added. In Example 1 in which 0.1 part by mass of silicone oil and 1 part by mass of DIDA were added, both of weather resistance and bleeding resistance were acceptable, but silicone oil and DIDA In Comparative Example 1 in which no addition was made, since cracks were generated after the weathering test and the appearance was unsatisfactory, the determination of weatherability was rejected.
또한 실시예2, 3 및 비교예2, 3은 DOTP의 첨가량이 40질량부, 100질량부인 경우로서, 실리콘오일을 0.1질량부 및 DIDA를 1질량부 첨가한 실시예2, 3은 실시예1과 마찬가지로 합격인 반면에, 실리콘오일 및 DIDA를 첨가하지 않은 비교예2, 3은 비교예1의 경우와 마찬가지로 외관이 불합격인 것 외에 신장잔율도 불합격이었기 때문에, 내후성의 판정은 불합격이었다.In Examples 2 and 3 and Comparative Examples 2 and 3, the addition amount of DOTP was 40 parts by mass and 100 parts by mass. Examples 2 and 3, in which 0.1 part by mass of silicone oil and 1 part by mass of DIDA were added, , Whereas Comparative Examples 2 and 3 in which silicone oil and DIDA were not added had the same appearance as in Comparative Example 1 and failed to determine the weatherability because the elongation percentage was also unsatisfactory.
이상으로부터, 실리콘오일 0.1질량부 이상 및 DIDA 등의 아디핀산 에스테르 1질량부 이상이 내후성과 내블리드성의 양립에 필요하다는 것을 볼 수 있었다.From the above, it can be seen that at least 0.1 part by mass of silicone oil and at least 1 part by mass of adipic acid ester such as DIDA are necessary for compatibility between weather resistance and bleeding resistance.
또한 실리콘오일을 1질량부 및 DIDA를 15질량부 첨가한 실시예4∼6에서는, 내후성·내블리드성 모두 합격이었다. 실리콘오일의 블리드를 DIDA 등의 아디핀산 에스테르의 첨가로 억제할 수 있었기 때문이다. 한편 실리콘오일 1질량부만을 첨가하고 DIDA를 첨가하지 않은 비교예4∼6에서는, 내후성은 개선되었지만, 블리드에 의한 표면에의 끈적임이 생겼다. 이로부터 실리콘오일과 DIDA 등의 아디핀산 에스테르 쌍방의 첨가가 아니면, 내후성의 개선 및 블리드의 억제가 양립하지 않는다는 것을 확인할 수 있었다.Further, in Examples 4 to 6 in which 1 part by mass of silicone oil and 15 parts by mass of DIDA were added, both weatherability and bleeding resistance were acceptable. This is because the bleeding of silicone oil can be suppressed by the addition of adipic acid ester such as DIDA. On the other hand, in Comparative Examples 4 to 6 in which only 1 part by mass of silicone oil was added and DIDA was not added, weather resistance was improved, but stickiness to the surface was caused by bleeding. From this, it was confirmed that the improvement of weatherability and the suppression of bleeding were incompatible with the addition of both the silicone oil and the adipic acid ester such as DIDA.
실시예6 및 비교예7로부터, DOTP는 100질량부를 넘으면 DOTP 자체가 블리드 해 버리기 때문에, DOTP의 첨가량은 100질량부가 한계라는 것을 알 수 있었다.From Example 6 and Comparative Example 7, it was found that the amount of DOTP added was 100 parts by mass because DOTP itself bleeds if DOTP exceeds 100 parts by mass.
실시예7∼9로부터, 실리콘오일을 2.5질량부 첨가하여도 내후성과 내블리드성이 양립할 수 있다는 것을 알 수 있었다. 또한 실시예10으로부터, DIDA를 30질량부 첨가하여도 내후성과 내블리드성이 양립할 수 있다는 것을 알 수 있었다.From Examples 7 to 9, it was found that even when 2.5 parts by mass of the silicone oil was added, the weather resistance and bleeding resistance were both compatible. From Example 10, it was also found that even when 30 parts by mass of DIDA was added, weatherability and bleed resistance were both compatible.
또한 실시예11∼16 및 비교예8, 9로부터, 테레프탈산 에스테르의 알킬쇄의 탄소수C8∼C10에서 상기의 결과와 같은 경향인 것을 볼 수 있었다. 또한 실시예5, 17, 18로부터, 아디핀산 에스테르의 알킬쇄의 탄소수C8∼C10에서 같은 경향인 것을 볼 수 있었다.From Examples 11 to 16 and Comparative Examples 8 and 9, it was also found that the carbon number of the alkyl chain of the terephthalic acid ester was in the range of C8 to C10, which is the same as the above results. From Examples 5, 17 and 18, it was also found that the alkyl chains of the adipic acid ester had the same C8-C10 carbon number.
또한 본 발명은, 상기 실시형태 및 실시예에 한정되지 않고 여러 가지로 변형하여 실시할 수 있다.
The present invention is not limited to the above-described embodiments and examples, and various modifications may be made.
1 : 도체
2 : 절연층
3 : 개재물
4 : 가압 테이프
5 : 시스
10 : 전선
20 : 케이블1: Conductor
2: Insulating layer
3: inclusions
4: Pressure tape
5: Cis
10: Wires
20: Cable
Claims (8)
염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 100질량부 이하, 실리콘오일(silicone oil)을 0.1질량부 이상, 아디핀산 에스테르(adipic acid ester)를 1질량부 이상 함유하는 염화비닐수지 조성물.
A vinyl chloride resin composition (PVC composition) containing a terephthalic acid ester as a plasticizer,
A vinyl chloride resin composition comprising 100 parts by mass or less of the terephthalic acid ester, 0.1 parts by mass or more of a silicone oil and 1 part or more of an adipic acid ester with respect to 100 parts by mass of a vinyl chloride resin.
염화비닐수지 100질량부에 대하여, 상기 실리콘오일을 0.1∼2.5질량부, 아디핀산 에스테르를 1∼30질량부 함유하는 염화비닐수지 조성물.
The method according to claim 1,
Wherein the vinyl chloride resin composition contains 0.1 to 2.5 parts by mass of the silicone oil and 1 to 30 parts by mass of adipic acid ester per 100 parts by mass of the vinyl chloride resin.
염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 10∼100질량부 함유하는 염화비닐수지 조성물.
3. The method according to claim 1 or 2,
A vinyl chloride resin composition containing 10 to 100 parts by mass of the terephthalic acid ester per 100 parts by mass of a vinyl chloride resin.
상기 테레프탈산 에스테르는, 1개당 알킬쇄(alkyl鎖; alkyl chain)의 탄소수가 8∼10인 테레프탈산 에스테르인 염화비닐수지 조성물.
The method according to any one of claims 1 to 3,
Wherein said terephthalic acid ester is a terephthalic acid ester having 8 to 10 carbon atoms in an alkyl chain per alkylene chain.
상기 아디핀산 에스테르는, 1개당 알킬쇄의 탄소수가 8∼10인 아디핀산 에스테르인 염화비닐수지 조성물.
The method according to any one of claims 1 to 4,
Wherein the adipic acid ester is an adipic acid ester having an alkyl chain of 8 to 10 carbon atoms per one molecule.
A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer is characterized by containing 100 parts by mass or less of the terephthalic acid ester, 0.1 parts by mass or more of a silicone oil and 1 part by mass or more of an adipic acid ester based on 100 parts by mass of a vinyl chloride resin An electric wire having an insulating layer made of a vinyl chloride resin composition.
A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer is characterized by containing 100 parts by mass or less of the terephthalic acid ester, 0.1 parts by mass or more of a silicone oil and 1 part by mass or more of an adipic acid ester based on 100 parts by mass of a vinyl chloride resin A cable having a sheath made of a vinyl chloride resin composition.
제6항의 전선을 구비한 케이블.8. The method of claim 7,
Cables having the electric wire of paragraph 6.
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| JPS5188543A (en) * | 1975-12-25 | 1976-08-03 | ENKABINIRUKEIJUSHISOSEIBUTSU OYOBISONOSEIZOHOHO | |
| JPS5954015B2 (en) * | 1979-12-27 | 1984-12-27 | 三菱化成ポリテック株式会社 | Manufacturing method of vinyl chloride resin film |
| JPS59145234A (en) * | 1983-02-09 | 1984-08-20 | Mitsui Toatsu Chem Inc | Lowly toxic agricultural vinyl chloride film |
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| JPH11302485A (en) * | 1998-04-27 | 1999-11-02 | Shin Etsu Polymer Co Ltd | Polyvinyl chloride resin composition and vehicle interior molding |
| CN102993602B (en) * | 2012-11-27 | 2014-08-06 | 宁波一舟塑胶有限公司 | CMP-grade flame-retardant smoke-inhibiting polyvinyl chloride cable sheath material and preparation method thereof |
| CN103509295B (en) * | 2013-10-12 | 2016-03-02 | 绿宝电缆（集团）有限公司 | A kind of environment-friendly heatproof composite elastic cable material for wires and cables |
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| WO2003002640A1 (en) * | 2001-06-29 | 2003-01-09 | Eastman Chemical Company | Pvc food wrap formed from dioctyl terphthalate plasticizer, method of forming same and method of wrapping food therewith |
| JP2003226788A (en) | 2002-02-06 | 2003-08-12 | Mitsubishi Chemicals Corp | Plasticizer composition and vinyl chloride resin composition |
| JP2009504851A (en) | 2005-08-12 | 2009-02-05 | イーストマン ケミカル カンパニー | Polyvinyl chloride composition |
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| JP2017019942A (en) | 2017-01-26 |
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| KR102517361B1 (en) | 2023-03-31 |
| JP6503947B2 (en) | 2019-04-24 |
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