KR20170008174A - 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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- 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
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- 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
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- 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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- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
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Abstract
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).
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)
그래서 본 발명은, 가소제로서 테레프탈산 에스테르를 사용하여도 내후성이 양호한 염화비닐수지 조성물, 및 이것을 사용한 전선 및 케이블을 제공하는 것을 목적으로 한다.
SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a vinyl chloride resin composition having excellent weather 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, 말단과 측쇄 중의 어느 한 개소 이상이 에폭시 변성된 폴리실록산을 0.1질량부 이상 함유하는 염화비닐수지 조성물.[1] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein a vinyl chloride resin composition containing 0.1 parts by mass or more of an epoxy-modified polysiloxane at any one or more of terminal and side chains relative to 100 parts by mass of a vinyl chloride resin .
[2] 염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 100질량부 이하 함유하는 상기 [1]에 기재되어 있는 염화비닐수지 조성물.[2] The vinyl chloride resin composition according to the above [1], which contains up to 100 parts by mass of the terephthalic acid ester with respect to 100 parts by mass of the vinyl chloride resin.
[3] 염화비닐수지 100질량부에 대하여, 상기 에폭시 변성된 폴리실록산을 0.1∼2.5질량부 함유하는 상기 [1] 또는 상기 [2]에 기재되어 있는 염화비닐수지 조성물.[3] The vinyl chloride resin composition according to the above [1] or [2], wherein the epoxy-modified polysiloxane is contained in an amount of 0.1 to 2.5 parts by mass based on 100 parts by mass of the vinyl chloride resin.
[4] 염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 10∼100질량부 함유하는 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], which contains 10 to 100 parts by mass of the terephthalic acid ester per 100 parts by mass of the vinyl chloride resin.
[5] 상기 테레프탈산 에스테르는, 1개당 알킬쇄의 탄소수가 8∼10인 테레프탈산 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 terephthalic acid ester is a terephthalic acid ester having an alkyl chain of 8 to 10 carbon atoms per one ester.
[6] 가소제로서 테레프탈산 에스테르를 함유하는 염화비닐수지 조성물에 있어서, 염화비닐수지 100질량부에 대하여, 말단과 측쇄 중의 어느 한 개소 이상이 에폭시 변성된 폴리실록산을 0.1질량부 이상 함유하는 염화비닐수지 조성물로 이루어지는 절연층을 구비한 전선.[6] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein a vinyl chloride resin composition containing 0.1 parts by mass or more of an epoxy-modified polysiloxane at any one or more of terminal and side chains, based on 100 parts by mass of the vinyl chloride resin And an insulating layer formed on the insulating layer.
[7] 가소제로서 테레프탈산 에스테르를 함유하는 염화비닐수지 조성물에 있어서, 염화비닐수지 100질량부에 대하여, 말단과 측쇄 중의 어느 한 개소 이상이 에폭시 변성된 폴리실록산을 0.1질량부 이상 함유하는 염화비닐수지 조성물로 이루어지는 시스를 구비한 케이블.[7] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein a vinyl chloride resin composition containing 0.1 parts by mass or more of an epoxy-modified polysiloxane at one or more of terminal and side chains relative to 100 parts by mass of a vinyl chloride resin And a sheath made up of the sheath.
[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 내후성이 양호한 염화비닐수지 조성물, 및 이것을 사용한 전선 및 케이블이 제공된다.
According to the present invention, a vinyl chloride resin composition having excellent weather 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, 말단(末端)과 측쇄(側鎖) 중의 어느 한 개소(個所) 이상이 에폭시 변성된 폴리실록산을 0.1질량부 이상 함유한다.The vinyl chloride resin composition according to the embodiment of the present invention is a vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer and is a vinyl chloride resin composition containing a vinyl chloride resin at one of terminal At least 0.1 part by mass of the epoxy-modified polysiloxane.
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, 에폭시 변성된 폴리실록산의 첨가를 검토하고, 테레프탈산 에스테르의 가수분해를 억제하는 것 등으로 내후성을 개선하는 본 발명을 발견하였다.Therefore, in order to suppress deterioration of weatherability when terephthalic acid ester is used, the present inventors have found that the addition of an epoxy-modified polysiloxane is studied and the hydrolysis of terephthalic acid ester is suppressed to improve weatherability.
(에폭시 변성된 폴리실록산)(Epoxy-modified polysiloxane)
본 발명의 실시형태에 관한 염화비닐수지 조성물로 사용되는 에폭시 변성된 폴리실록산은, 하기의 식(3)으로 나타내는 말단과 측쇄 중의 어느 한 개소 이상이 에폭시 변성된 것임을 특징으로 한다. 식 중의 m, n은 1 이상의 정수, A는 CH3 또는 에폭시기를 나타낸다. 또한 A 중의 어느 한 개소 이상에 에폭시기를 구비한다. 에폭시기의 위치는, 한쪽 말단에만, 양쪽 말단에만, 측쇄에만, 한쪽 말단과 측쇄, 양쪽 말단과 측쇄 중의 어느 쪽으로 하여도 좋다.The epoxy-modified polysiloxane used in the vinyl chloride resin composition according to the embodiment of the present invention is characterized in that at least one of the terminal and side chain represented by the following formula (3) is epoxy-modified. In the formula, m and n are integers of 1 or more, and A represents CH 3 or an epoxy group. And an epoxy group is provided at one or more of the A sites. The position of the epoxy group may be located at only one end, only the both ends, only the side chain, one end and the side chain, both ends and the side chain.
(화학식3)(Formula 3)
폴리실록산은, PVC 조성물로서 상용(相溶)되기 어렵지만, 에폭시 변성시킴으로써 극성이 커져 PVC-가소제 간에 상용되기 쉬워진다. 그 때문에 가소제 근방에서 실리콘오일의 발수능력에 의하여 가소제의 가수분해 억제에 작용함과 아울러, 에폭시기에 의한 염화비닐수지 자체의 탈염산 억제에도 작용한다. 이 내수성(耐水性)과 내광성(耐光性)의 상승작용에 의하여, 내후성의 열화의 억제에 강하게 기능한다고 생각된다.The polysiloxane is difficult to be compatibilized as a PVC composition, but when the epoxy is modified, the polysiloxane becomes polar and becomes easily compatible with PVC-plasticizers. Therefore, it acts to suppress the hydrolysis of the plasticizer by the water-repelling ability of the silicone oil in the vicinity of the plasticizer, and also acts to inhibit dehydrochlorination of the vinyl chloride resin itself by the epoxy group. It is believed that it functions strongly to suppress deterioration of weatherability by synergy effect of water resistance and light resistance.
본 발명의 실시형태에 있어서 상기 폴리실록산의 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, 에폭시 변성된 폴리실록산 자체가 블리드(bleed)하여 표면에 끈적임이 발생하기 때문이다.In the embodiment of the present invention, the addition amount of the polysiloxane 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. When the amount exceeds 2.5 parts by mass, the epoxy-modified polysiloxane itself is bleed and sticky to the surface occurs.
(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 이하가 바람직하고, 10∼100질량부가 더 바람직하다. 에폭시 변성 폴리실록산을 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 preferably 100 parts by mass or less, more preferably 10 to 100 parts by mass, per 100 parts by mass of the vinyl chloride resin. The addition of the epoxy-modified polysiloxane exerts an effect on the addition of the terephthalic acid ester, but if the addition amount of the terephthalic acid ester exceeds 100 parts by mass, the plasticizer itself bleeds and stickiness occurs on the surface.
(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, 아디핀산 에스테르, 에폭시화 대두유 등의 다른 가소제를 블렌드하여 사용하여도 좋다.For example, when it is desired to improve heat resistance, cold resistance, insulation, etc., other plasticizers such as phthalic acid ester, isophthalic acid ester, trimellitic acid ester, pyromellitic acid ester, adipic acid ester and epoxidized soybean oil are blended May be used.
〔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, 폴리실록산(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.A plasticizer, a polysiloxane (silicone oil) as a ratio shown in Tables 1 to 3, a calcium-zinc lead-free lead-free stabilizer as a stabilizer, and calcium carbonate as a filler were mixed with 100 parts by mass of PVC having an average degree of polymerization of 1300. 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)
(3) 폴리실록산(실리콘오일) : 신에쓰 실리콘(Shin-Etsu Silicone) 제품(3) Polysiloxane (silicone oil): Shin-Etsu Silicone products
측쇄 에폭시 변성 폴리실록산(상품명 : X-22-343)Side chain epoxy-modified polysiloxane (trade name: X-22-343)
한쪽 말단 에폭시 변성 폴리실록산(상품명 : X-22-173DX)One-end epoxy-modified polysiloxane (trade name: X-22-173DX)
양쪽 말단 에폭시 변성 폴리실록산(상품명 : X-22-163B)Both ends of the epoxy-modified polysiloxane (trade name: X-22-163B)
측쇄 및 양쪽 말단 에폭시 변성 폴리실록산(상품명 : X-22-9002)Side chain and both-end epoxy-modified polysiloxane (trade name: X-22-9002)
(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, 에폭시 변성된 폴리실록산을 0.1질량부 첨가한 실시예1에서는 내후성·내블리드성 모두 합격이었지만, 에폭시 변성된 폴리실록산을 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 parts by mass of the epoxy-modified polysiloxane was added, both of weather resistance and bleeding resistance were acceptable. However, In Example 1, since a crack occurred 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, 에폭시 변성된 폴리실록산을 0.1질량부 첨가한 실시예2, 3은 실시예1과 마찬가지로 합격인 반면에, 에폭시 변성된 폴리실록산을 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, and in Examples 2 and 3 in which 0.1 parts by mass of the epoxy-modified polysiloxane was added, On the other hand, in Comparative Examples 2 and 3 in which the epoxy-modified polysiloxane was not added, the appearance was rejected and the elongation percentage was also unacceptable as in the case of Comparative Example 1. Therefore, the determination of weatherability was rejected.
또한 실시예4∼6 및 비교예4∼6은 DINTP를 10∼100질량부 첨가한 경우로서, DOTP를 첨가한 실시예1∼3 및 비교예1∼3의 경우와 마찬가지의 결과를 나타냈다.In Examples 4 to 6 and Comparative Examples 4 to 6, 10 to 100 parts by mass of DINTP was added, and the same results as in Examples 1 to 3 and Comparative Examples 1 to 3 in which DOTP was added were shown.
또한 실시예7∼9 및 비교예7∼9는 DIDTP를 10∼100질량부 첨가한 경우로서, DOTP를 첨가한 실시예1∼3 및 비교예1∼3의 경우와 마찬가지의 결과를 나타냈다.In Examples 7 to 9 and Comparative Examples 7 to 9, 10 to 100 parts by mass of DIDTP was added, and the same results as in Examples 1 to 3 and Comparative Examples 1 to 3 in which DOTP was added were shown.
이상으로부터, 에폭시 변성된 폴리실록산은 0.1질량부 이상이 필요하다는 것을 볼 수 있었다. 또한 테레프탈산 에스테르 가소제는 알킬쇄의 탄소수C8∼C10에서 같은 경향인 것을 볼 수 있었다.From the above, it can be seen that at least 0.1 part by mass of the epoxy-modified polysiloxane is required. It was also found that the terephthalate ester plasticizer had the same tendency in the C 8 -
실시예13 및 18의 비교로부터, 에폭시 변성된 폴리실록산의 첨가량이 2.5질량부를 넘으면, 내후성은 개선되지만, 블리드에 의한 표면에의 끈적임이 생긴다는 것을 볼 수 있었다.From the comparison of Examples 13 and 18, it was found that when the addition amount of the epoxy-modified polysiloxane exceeds 2.5 parts by mass, the weather resistance is improved but the surface is tacky due to bleeding.
또한 실시예3 및 17의 비교로부터, DOTP의 첨가량이 100질량부를 넘으면, 에폭시 변성된 폴리실록산의 첨가로 내후성은 개선되지만, 블리드에 의한 표면에의 끈적임이 생긴다는 것을 볼 수 있었다.Further, from the comparison of Examples 3 and 17, it was found that when the addition amount of DOTP exceeds 100 parts by mass, the weather resistance is improved by the addition of the epoxy-modified polysiloxane, but stickiness to the surface is caused by the bleeding.
또한 실시예1∼20으로부터, 폴리실록산의 말단과 측쇄 중의 어느 한 개소 이상이 에폭시 변성되어 있으면, 어느 것을 첨가한 경우에도 내후성이 개선된다는 것을 볼 수 있었다.From Examples 1 to 20, it was also found that when any one or more of the terminal and side chains of the polysiloxane is epoxy-modified, the weather resistance is improved even when any one is added.
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, 말단(末端)과 측쇄(側鎖) 중의 어느 한 개소(個所) 이상이 에폭시 변성된 폴리실록산(epoxy-modified polysiloxane)을 0.1질량부 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 an epoxy-modified polysiloxane in an amount of 0.1 part by mass or more based on 100 parts by mass of a vinyl chloride resin, wherein at least one of terminal and side chains is epoxy-modified polysiloxane.
염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 100질량부 이하 함유하는 염화비닐수지 조성물.
The method according to claim 1,
A vinyl chloride resin composition containing 100 parts by mass or less of the terephthalic acid ester with respect to 100 parts by mass of a vinyl chloride resin.
염화비닐수지 100질량부에 대하여, 상기 에폭시 변성된 폴리실록산을 0.1∼2.5질량부 함유하는 염화비닐수지 조성물.
3. The method according to claim 1 or 2,
Wherein the vinyl chloride resin composition contains 0.1 to 2.5 parts by mass of the epoxy-modified polysiloxane based on 100 parts by mass of the vinyl chloride resin.
염화비닐수지 100질량부에 대하여, 상기 테레프탈산 에스테르를 10∼100질량부 함유하는 염화비닐수지 조성물.
The method according to any one of claims 1 to 3,
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 4,
Wherein said terephthalic acid ester is a terephthalic acid ester having 8 to 10 carbon atoms in an alkyl chain per alkylene chain.
A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer is characterized in that the vinyl chloride resin composition comprises 100 parts by mass of vinyl chloride resin composition comprising 100 parts by mass of a vinyl chloride resin composition containing 0.1 parts by mass or more of a polysiloxane in which at least one of terminal and side chains is epoxy- An electric wire having an insulating layer.
A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer is characterized by comprising a vinyl chloride resin composition comprising 100 parts by mass of a vinyl chloride resin composition containing 0.1 parts by mass or more of an epoxy modified polysiloxane at one or more of terminal and side chains A cable with a sheath.
제6항의 전선을 구비한 케이블.8. The method of claim 7,
Cables having the electric wire of paragraph 6.
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| JPH06299025A (en) * | 1993-04-20 | 1994-10-25 | Shin Etsu Chem Co Ltd | Vinyl chloride resin composition |
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| 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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| JPS59145234A (en) * | 1983-02-09 | 1984-08-20 | Mitsui Toatsu Chem Inc | Lowly toxic agricultural vinyl chloride film |
| JPS6299025A (en) * | 1985-10-25 | 1987-05-08 | Hitachi Ltd | Parts pressing mechanism |
| JP2003226788A (en) | 2002-02-06 | 2003-08-12 | Mitsubishi Chemicals Corp | Plasticizer composition and vinyl chloride resin composition |
| JP2014159507A (en) | 2013-02-19 | 2014-09-04 | Hitachi Metals Ltd | Flame-retardant vinyl chloride resin composition, insulated wire, and cable |
| CN103509293A (en) * | 2013-10-12 | 2014-01-15 | 绿宝电缆（集团）有限公司 | Environment-friendly cold-resistant polyvinyl chloride cable material |
| JP2015089934A (en) | 2013-11-07 | 2015-05-11 | ダイキン工業株式会社 | Flame-retardant resin composition, molded product, wire and jacket |
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