KR20010081717A - Silicon-rubber composition for printing and curing method there - Google Patents

Silicon-rubber composition for printing and curing method there Download PDF

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KR20010081717A
KR20010081717A KR1020000007792A KR20000007792A KR20010081717A KR 20010081717 A KR20010081717 A KR 20010081717A KR 1020000007792 A KR1020000007792 A KR 1020000007792A KR 20000007792 A KR20000007792 A KR 20000007792A KR 20010081717 A KR20010081717 A KR 20010081717A
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parts
weight
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silicone
printing
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김성수
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김성수
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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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen

Abstract

PURPOSE: Provided are a printing silicone rubber composition and its hardening method. The composition has good adhesiveness and the same hardness as human skin. It is not harmful to human body when contacted, felt and worn as printed letters or figures on the cotton or polyester clothing. CONSTITUTION: The composition comprises 100wt. parts silicone liquid rubber of chemical formula I or II, where V is vinyl group and R is C1-7 alkyl group and n is mol. wt. of 10,000-250,000, 8-15wt. parts of polydimethylsiloxane oil with viscosity under 10cps, 2-10wt. parts of epoxysilane, 0.5-1.0wt. parts of aminosilane, 0.1-0.4wt. parts of Pt catalyst, 0.4-1.0wt. parts of pigments, 1-8wt. parts of CaCO3 and 2-10wt. parts of silica of 200 or 300 in mesh size. The composition is hardened by radical reaction of atoms in a wanted thickness by heating 2-15 second interval on cotton fiber by screen printing method at 100-150 deg.C and under 50-80% moisture.

Description

인쇄용 실리콘 고무조성물 및 그의 경화방법{Silicon-rubber composition for printing and curing method there}Silicone rubber composition for printing and curing method thereof {Silicon-rubber composition for printing and curing method there}

본 발명은 합성섬유 및 천연섬유 등의 표면에 사용되는 인쇄용 실리콘 고무조성물 및 그의 경화방법에 관한 것이다.The present invention relates to a silicone rubber composition for printing used on surfaces of synthetic fibers and natural fibers, and a curing method thereof.

보다 구체적으로는 면등의 천연 섬유나 폴리에스터등의 합성섬유로 된 양말, 모자, 가방, 장식용 테이프, 목걸이줄, 핸드폰고리, 신발, 지퍼고리 또는 의류용 원단이나 합성피혁 등에 문자, 도형 또는 기호 등의 표시를 형성하는 인쇄용 실리콘 고무조성물 및 그의 경화방법에 관한 것이다.More specifically, letters, figures, or symbols such as socks, hats, bags, decorative tapes, necklaces, cell phone rings, shoes, zipper rings or clothing fabrics or synthetic leathers are made of natural fibers such as cotton or synthetic fibers such as polyester. It relates to a silicone rubber composition for printing and a curing method thereof for forming a mark.

종래에는 양말이나 의류에 사용되는 섬유이나 피혁등에 실크 스크린 인쇄법으로 문자,도형 또는 기호나 이들의 결합으로 이루어진 표시를 형성하는데 아크릴 수지 또는 폴리우레탄 수지를 이용한 잉크나 플라스틱졸(Sol) 즉, PVC졸을 함유한 PVC잉크를 사용하였다. 이러한 아크릴, 폴리우레탄 또는 PVC잉크를 이용하여 섬유 등의 표면에 문자등의 디자인이 형성된 섬유나 의복을 만들었을 경우 인체에 접촉시 촉감, 착용감과 피부 밀착성이 좋았다.Conventionally, a silk or a silk screen printing method is used to form a mark composed of letters, figures, symbols, or a combination thereof. PVC ink containing sol was used. When acrylic or polyurethane or PVC ink was used to make fibers or garments with letters, etc., on the surfaces of the fibers, the touch, fit and skin adhesion were good when they were in contact with the human body.

그러나, 아크릴 또는 폴리우레탄 수지등을 사용한 경우에는 독성물질이 함유되어 인체에 해를 주며, PVC졸을 이용한 경우에는 PVC졸에 가소제로서 DOP, DBP를 사용함으로 인하여 인체에 해를 끼칠 수 있었다. 그리고 최근에는 유럽에서 아기용 양말등에 미끄럼을 방지하기 위해 사용하는 넌슬립(Nonslip)부분에 환경호르몬을 일으키는 물질의 사용을 규제하고 있어서 이에 대한 대체물질이 요구되고 있다.However, when acrylic or polyurethane resins are used, toxic substances are contained and harmful to the human body. When the PVC sol is used, the PVC sol may harm the human body by using DOP and DBP as plasticizers. Recently, in Europe, non-slip parts used to prevent slipping in baby socks, etc., regulate the use of substances that cause environmental hormones, and alternative materials are required.

또 다른 방법으로서 실리콘잉크를 사용하고 있다. 이 실리콘 잉크를 사용하였을 경우 쇼아(Shore A) 경도가 30∼50의 고경도이므로 인체에 접촉시 딱딱하여 촉감자체가 좋지 않고 착용감 및 피부 밀착성이 좋지 않다. 특히 나일론사, PET(Poly Ethylene Terephtalate)사, 폴리원사 등으로 된 원단등에는 접착이 불량하여 사용이 불가능하였다.Another method uses silicon ink. When the silicone ink is used, the Shore A has a high hardness of 30 to 50, so it is hard to touch the human body, and thus the touch itself is not good and the fit and skin adhesion are poor. In particular, fabrics made of nylon, PET (Poly Ethylene Terephtalate), poly yarns, etc. were not used because of poor adhesion.

본 발명은 이러한 문제점을 해결하기 위한 것으로, 사람의 피부와 동일한 경도를 가지면서 인체에 접촉시 촉감, 착용감 및 피부 밀착성은 물론 인체에 전혀 해가 없는 디자인 형성 등의 인쇄용 실리콘 조성물 및 그의 경화방법을 제공하고자 한다.The present invention has been made to solve the above problems, while having the same hardness as the human skin and the touch, the fit and skin contact when contacting the human body as well as the printing silicone composition and the curing method thereof, such as forming a design that does not harm the human body at all To provide.

이하, 본 발명의 구성 및 작용효과를 상세히 설명하면 다음과 같다.Hereinafter, the configuration and effect of the present invention will be described in detail.

본 발명의 조성물은 실리콘 액상고무 100중량부에 대하여 실리콘 오일 8∼15중량부, 에폭시실란 2∼10중량부, 아미노실란 0.5∼1.0중량부, 백금촉매 0.1∼0.4 중량부, 안료 0.3∼1.0 중량부, 탄산칼슘(CaCO₃) 1∼8중량부, 실리카 200 메시 또는 300메시 2∼10중량부로 구성된다.The composition of the present invention is 8 to 15 parts by weight of silicone oil, 2 to 10 parts by weight of epoxy silane, 0.5 to 1.0 part by weight of aminosilane, 0.1 to 0.4 part by weight of platinum catalyst, and 0.3 to 1.0 weight of pigment based on 100 parts by weight of silicone liquid rubber. It is composed of 1 to 8 parts by weight of calcium carbonate (CaCO 3), 2 to 10 parts by weight of silica 200 mesh or 300 mesh.

실리콘 액상고무는 다음 화학식 1 또는 2(상기 식 (I),(II)중에서 V는 비닐기(-CH=CH2)를 나타내며, R은 탄소수가 1 ∼7인 알킬기이며, n은 분자량이 1만 내지 25만이다.)으로 나타내는 화합물을 사용한다.The silicone liquid rubber is represented by the following Chemical Formula 1 or 2 (In Formulas (I) and (II), V represents a vinyl group (-CH = CH 2 ), R is an alkyl group having 1 to 7 carbon atoms, and n has a molecular weight of 1). 10,000 to 250,000.).

실리콘 오일은, 폴리디메틸실록산 오일로서 점도가 10cps이하인 오일을 사용하는 것이 바람직하다. 이 오일은 본 발명의 조성물에 첨가되어 고무의 경도를 저하시켜서 유연성을 크게 향상시킨다. 첨가량은 8∼15중량부를 사용하며, 8중량부 미만이면 경화시 딱딱하여 경도가 높고, 15중량부를 초과하면 고가이므로 경제성이떨어지며 작업성이 좋지 않다.It is preferable that silicone oil uses the oil whose viscosity is 10 cps or less as polydimethylsiloxane oil. This oil is added to the composition of the present invention to lower the hardness of the rubber, thereby greatly improving the flexibility. The addition amount is used 8 to 15 parts by weight, less than 8 parts by weight is hard at the time of curing, high hardness, when exceeding 15 parts by weight is expensive and the economic efficiency is poor and workability is not good.

에폭시 실란 또는 아미노 실란은, 화학식 3으로 나타내는 화합물을 말한다.Epoxy silane or amino silane means the compound represented by General formula (3).

상기 식중에서 X는 에폭시기 또는 아미노기를 나타내며, OR은 메톡시기 또는 에톡시기를 나타낸다. 에폭시 실란 및 아미노 실란은 일반적으로 시중에서 사용되는 것이면 모두 사용가능하며, 접착성을 크게 향상시킨다. 실리콘 액상 고무와 함께 사용되어 시너지 효과를 극대화시켜 주며, 면섬유는 물론 나일론사, PET사, 폴리원단등의 합성섬유에도 접착강도를 크게 높여준다.In said formula, X represents an epoxy group or an amino group, and OR represents a methoxy group or an ethoxy group. Epoxy silanes and amino silanes are generally available as long as they are commercially available and greatly improve adhesion. Used in conjunction with silicone liquid rubber, it maximizes synergy effect and greatly improves adhesive strength not only for cotton fiber but also synthetic fiber such as nylon, PET and poly fabric.

에폭시 실란은 2-10중량부를 사용하며, 2중량부 미만이면 접착성이 떨어지고 10중량부를 초과하면 경제성이 떨어진다. 아미노 실란은 0.5∼1.0 중량부를 사용하며, 접착성이 떨어지고 10중량부를 초과하면 고가이므로 경제성이 떨어진다Epoxy silane is used in 2-10 parts by weight, less than 2 parts by weight of the adhesion is poor, more than 10 parts by weight of economic efficiency. Amino silane is used in the range of 0.5 to 1.0 parts by weight, and is inferior in adhesiveness.

안료는 필요에 따라 무기안료 또는 유기안료를 선택적으로 사용할 수 있다. 첨가량은 0.3∼1.0중량부를 사용하며 그 이상도 가능하다. 탄산칼슘은 1∼8중량부를 사용하며 8중량부를 초과하면 신도, 인장력이 저하된다.The pigment may optionally use an inorganic pigment or an organic pigment, as necessary. The addition amount is 0.3 to 1.0 parts by weight, and more than that is possible. Calcium carbonate is used in an amount of 1 to 8 parts by weight, and when it exceeds 8 parts by weight, elongation and tensile strength decrease.

실리카는 접착성을 크게 향상시키며 크기는 200메시 또는 300메시의 입자를사용하되 첨가량은 2-10중량부를 첨가한다. 2중량부 미만이면, 접착성이 떨어지고 점도가 낮아 작업성이 좋지 않으며,10중량부를 초과하면 신도, 인장력이 저하되고 경도가 높아진다.Silica greatly improves the adhesion and the size of 200 mesh or 300 mesh particles are used, the addition amount is added 2-10 parts by weight. If it is less than 2 parts by weight, the adhesiveness is low and the viscosity is low, and workability is not good. If it exceeds 10 parts by weight, elongation and tensile strength are lowered, and hardness is increased.

실리콘을 이용하여 실리콘 고무 조성물을 경화하는 방법은 일반적으로 축합 반응에 의한 방법과 부가 반응에 의한 방법이 있다. 축합반응은 물과 반응하여 경화물을 형성한다. 부가반응은 또한 여러 가지 방법이 있다.The method of hardening a silicone rubber composition using silicone generally has the method by the condensation reaction and the method by the addition reaction. The condensation reaction reacts with water to form a cured product. There are also several ways of addition reactions.

본 발명은 촉매하에서 일정한 온도를 가하여 원자의 래디칼 반응으로 이루어지는 경화방법으로서, 암모니아에 의해 치환된 액상의 백금촉매 또는 그밖의 백금화합물류를 첨가하여 습도 50∼80%, 온도100∼150℃의 조건하에서 두께에 따라서 2초∼15초의 간격으로 경화시켜 원하는 실리콘 고무가 일체로 부착된 섬유로된 양말 등을 제조하는 방법이다.The present invention is a curing method consisting of radical reactions of atoms by applying a constant temperature under a catalyst, wherein a liquid platinum catalyst substituted with ammonia or other platinum compounds is added to a humidity of 50 to 80% and a temperature of 100 to 150 ° C. It is a method of manufacturing socks and the like made of fibers to which the desired silicone rubber is integrally attached by curing at intervals of 2 to 15 seconds depending on the thickness.

실시예1Example 1

비닐기가 양말단에 부착되고 분자량이 20만인 실리콘액상고무 100중량부에 대하여 점도가 10cps인 폴리디메틸실록산 오일 9중량부, 에폭시실란 5중량부, 아미노산실란 0.8중량부, 청색유기안료 0.4중량부, 탄산칼슘 3중량부, 실리카 200메시 8중량부를 교반기로 혼합한 후, 인쇄시 사용직전에 백금촉매 0.4중량부를 넣고 스크린 인쇄하였다.9 parts by weight of polydimethylsiloxane oil having a viscosity of 10 cps, 5 parts by weight of epoxy silane, 0.8 parts by weight of amino acid silane, 0.4 parts by weight of blue organic pigment, with respect to 100 parts by weight of a silicone liquid rubber having a molecular weight of 200,000 After mixing 3 parts by weight of calcium carbonate and 8 parts by weight of silica 200 mesh with a stirrer, 0.4 parts by weight of a platinum catalyst was added immediately before use in printing and screen printed.

경화된 실리콘 경도 9°로서 사람의 피부와 거의 동일하였으며, 촉감 및 착용감은 물론 접착성이 매우 양호하였다.The cured silicone hardness of 9 ° was almost the same as that of human skin, and the adhesion as well as the feel and fit were very good.

실시예2Example 2

실시예1의 조성물을 습도 80%, 온도 150℃ 조건하에서 스크린 인쇄방법으로 면섬유에 70미크론의 두께를 형성한 후, 3초 동안 가열하였다.The composition of Example 1 was formed with a thickness of 70 microns on cotton fibers by screen printing under a condition of humidity of 80% and a temperature of 150 ° C., and then heated for 3 seconds.

경화된 실리콘 경도는 실시예1과 마찬가지로 접착성이 양호하였으며, 촉감 및 착용감이 좋았다.The cured silicone hardness had good adhesion as in Example 1, and had a good feel and fit.

이상과 같이 얻은 본 발명은 경화된 실리콘의 경도가 10°로, 사람의 피부와 동일한 경도를 나타내며, 인체에 접촉시 촉감, 착용감 및 피부 밀착성이 좋으며, 직조원단등의 표면과 접착성이 매우 좋았다.In the present invention obtained as described above, the hardness of the cured silicone is 10 °, showing the same hardness as human skin, good touch, fit and skin adhesion when in contact with the human body, very good adhesion to the surface, such as woven fabrics .

Claims (2)

다음 화학식(I)또는(II)인 실리콘 액상고무 100중량부에 대하여 점도가 10cps이하인 폴리 디메틸 실록산 오일 8∼15중량부, 에폭시 실란 2∼10중량부, 아미노 실란 0.5∼1.0중량부, 백금촉매 0.1∼0.4 중량부, 안료 0.4∼1.0 중량부, 탄산칼슘(CaCO₃)1∼8중량부, 실리카 200 메시 또는 300메시 2∼10중량부로 이루어진 것을 특징으로 하는 인쇄용 실리콘 고무조성물.8 to 15 parts by weight of polydimethyl siloxane oil having a viscosity of 10 cps or less, 2 to 10 parts by weight of epoxy silane, 0.5 to 1.0 part by weight of amino silane, and platinum catalyst based on 100 parts by weight of silicone liquid rubber of formula (I) or (II) 0.1 to 0.4 parts by weight, pigment 0.4 to 1.0 part by weight, calcium carbonate (CaCO₃) 1 to 8 parts by weight, silica 200 mesh or 2 to 10 parts by weight of 300 mesh printing silicone rubber composition. 화학식 1 또는 화학식 2Formula 1 or Formula 2 (상기 식 (I),(II)중에서 V는 비닐기(-CH=CH2)를 나타내며, R은 탄소수가 1- 7인 알킬기이며, n은 분자량이 1만 내지 25만이다.)(In the formulas (I) and (II), V represents a vinyl group (-CH = CH 2 ), R is an alkyl group having 1 to 7 carbon atoms, and n has a molecular weight of 10,000 to 250,000.) 촉매의 첨가하에서 온도를 가하여 원자의 래디칼 반응으로 경화함에 있어서, 백금촉매, 습도 50∼80%, 온도 100∼150℃의 조건하에서 두께에 따라서 2초∼15초의 간격으로 경화시켜 됨을 특징으로 하는 인쇄용 실리콘 고무의 경화방법.For curing by radical reaction of atoms by adding temperature under the addition of a catalyst, it is cured at intervals of 2 to 15 seconds depending on the thickness under the conditions of platinum catalyst, humidity of 50 to 80% and temperature of 100 to 150 ° C. Method of curing silicone rubber.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100756332B1 (en) * 2001-12-21 2007-09-06 (주)브레인유니온시스템 Complex highmolecular resin composition and printed matter surface treating method therewith
KR101152180B1 (en) * 2010-08-25 2012-06-15 주식회사 케이씨씨 Silicone rubber composition for forming a pattern on fabric or cloth
KR102525342B1 (en) * 2022-11-22 2023-04-26 (주)성원피앤에스 Pigment composition for silicone rubber composition comprising filler complex and method for manufacturing the same

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JPH03292370A (en) * 1990-04-10 1991-12-24 Ricoh Co Ltd Coloring agent
JPH04175387A (en) * 1990-11-08 1992-06-23 Nippon Hikyumen Lens Kk Coating composition for hard coat being post-printable
JPH08134394A (en) * 1994-11-11 1996-05-28 Toshiba Silicone Co Ltd Coating composition for rubber-coated fabric

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03292370A (en) * 1990-04-10 1991-12-24 Ricoh Co Ltd Coloring agent
JPH04175387A (en) * 1990-11-08 1992-06-23 Nippon Hikyumen Lens Kk Coating composition for hard coat being post-printable
JPH08134394A (en) * 1994-11-11 1996-05-28 Toshiba Silicone Co Ltd Coating composition for rubber-coated fabric

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100756332B1 (en) * 2001-12-21 2007-09-06 (주)브레인유니온시스템 Complex highmolecular resin composition and printed matter surface treating method therewith
KR101152180B1 (en) * 2010-08-25 2012-06-15 주식회사 케이씨씨 Silicone rubber composition for forming a pattern on fabric or cloth
KR102525342B1 (en) * 2022-11-22 2023-04-26 (주)성원피앤에스 Pigment composition for silicone rubber composition comprising filler complex and method for manufacturing the same

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