KR100776312B1 - Primer composition for metal-plastic bonding - Google Patents
Primer composition for metal-plastic bonding Download PDFInfo
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- KR100776312B1 KR100776312B1 KR1020060034519A KR20060034519A KR100776312B1 KR 100776312 B1 KR100776312 B1 KR 100776312B1 KR 1020060034519 A KR1020060034519 A KR 1020060034519A KR 20060034519 A KR20060034519 A KR 20060034519A KR 100776312 B1 KR100776312 B1 KR 100776312B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/16—Esters of inorganic acids
- C08L1/18—Cellulose nitrate, i.e. nitrocellulose
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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
- C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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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
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/163—Metal in the substrate
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Abstract
본 발명은 용융 사출온도가 250~350℃인 플라스틱을 250~350℃에서 금속표면에 사출하여 금속과 플라스틱을 접착시키는 인몰드접착방법에서 금속표면에 도포하는 프라이머 조성물에 있어서, 열경화성수지 20~30wt%, 열가소성수지 20~30wt%, 용제 40~60wt%로 조성된 주재 95~97wt%에 대하여 경화제로서 디페닐메탄디이소시아네이트 3~5wt%를 첨가하여서 조성된 금속-플라스틱 접착용 프라이머 조성물에 관한 것이다.The present invention is a primer composition which is applied to the metal surface in the in-mold bonding method for bonding the metal and plastic by injecting a plastic with a melt injection temperature of 250 ~ 350 ℃ to the metal surface at 250 ~ 350 ℃, 20 ~ 30wt %, Thermoplastic resin 20-30 wt%, solvent 40-60 wt%, based on 95-97 wt% of a main ingredient, a metal-plastic adhesive primer composition prepared by adding 3-5 wt% of diphenylmethane diisocyanate as a curing agent. .
본 발명의 조성물은 인몰드방식으로 금속-플라스틱을 접착시켜줄 때 금속표면에 도포하여 금속-플라스틱간의 접착력이 우수한 성형물을 얻을 수 있는 효과가 있다.The composition of the present invention has an effect of obtaining a molded article having excellent adhesion between the metal and the plastic by applying to the metal surface when the metal-plastic is bonded in an in-mold manner.
프라이머조성물, 금속-플라스틱 접착, 인몰드접착, 열경화성수지, 열가소성수지 Primer Composition, Metal-Plastic Bonding, In Mold Bonding, Thermosetting Resin, Thermoplastic Resin
Description
도 1은 종래 인몰드 방식으로 금속판과 플라스틱을 접착시키는 공정에서 플라스틱 사출금형의 단면을 나타낸 도면이다.1 is a cross-sectional view of a plastic injection mold in a process of bonding a metal plate and a plastic in a conventional in-mold method.
- 도면중 중요부분에 대한 부호의 설명 - -Explanation of symbols for important parts of drawings-
1 : 금속판 4 : 플라스틱 주입구1: metal plate 4: plastic injection hole
2 : 접착필름 5 : 금형2: adhesive film 5: mold
3 : 플라스틱이 채워질 공간3: space to be filled with plastic
본 발명은 금속-플라스틱 접착용 프라이머(primer) 조성물에 관한 것이다.The present invention relates to a primer composition for metal-plastic adhesion.
구체적으로는 인몰드(inmold) 접착방식으로 금속과 플라스틱을 접착시켜줄 때 금속과 플라스틱의 접착을 용이하게 하여주기 위해서 금속표면에 도포하는 금속-플라스틱 접착용 프라이머 조성물에 관한 것이다.Specifically, the present invention relates to a primer composition for metal-plastic adhesion, which is applied to a metal surface in order to facilitate the adhesion of metal and plastic when the metal and plastic are adhered by an inmold adhesion method.
핸드폰(handphone), 이어폰(earphone) 또는 MP3와 같은 소형전자제품의 하우 징(housing : 부품, 장치등을 수용하는 상자형 부품)에는 금속과 플라스틱을 접착시켜 일체로 성형하여서 된 판상의 소재가 많이 사용되고 있다.The housing of small electronic products such as mobile phones, earphones, or MP3s is a box-shaped material formed by bonding metal and plastic together to form a unit. It is used.
소형 전자제품의 하우징을 금속-플라스틱 접착제품으로 구성시켜주는 이유는 외관이 미려하면서 부드럽고 두께가 얇으면서 일정한 강도를 유지시켜주기 위한 것이다.금속판만으로는 두께가 얇고 강도가 높은 제품을 제조할 수는 있으나 부드럽고 미려한 외관을 나타나게 하는데 한계가 있으며 플라스틱만으로는 두께가 얇으면서 높은 강도를 유지할 수 있는 제품을 얻기 어렵기 때문에 금속-플라스틱 복합재를 이 분야에서 많이 이용하고 있다.The reason why the housing of small electronic products is composed of metal-plastic adhesive is to keep the strength while maintaining the strength while maintaining the strength. Metal-plastic composites are widely used in this field because there is a limit to the appearance of a soft and beautiful appearance, and it is difficult to obtain a product that can maintain a high strength with thin thickness only by plastic alone.
핸드폰용 하우징의 경우 두께 0.1~0.4㎜인 금속판에 두께 0.1~1.5㎜인 플라스틱을 접착시켜서 구성된 소재가 많이 이용되고 있다.In the case of a mobile phone housing, a material composed by bonding a plastic having a thickness of 0.1 to 1.5 mm to a metal plate having a thickness of 0.1 to 0.4 mm is used.
종래 휴대폰용 하우징은 도1에 도시한 바와 같이 두께 0.1~0.4㎜인 금속판(1)에 두께 0.05~0.1㎜의 필름상으로 형성시킨 접착필름(2)을 접착시킨 후 이를 금형(5)에 넣고 접착 필름면에 플라스틱의 두께가 0.1~1.5㎜되도록 플라스틱을 플라스틱주입구(4)로 사출하여 금속과 플라스틱이 접착된 하우징을 제조한다.In the conventional mobile phone housing, as shown in FIG. 1, the
여기에 사용되는 금속으로서는 철 또는 동이나 철 또는 동에 크롬, 니켈, 금, 은으로 도금된 제품이 주로 사용되고 있으며 플라스틱으로서는 폴리카보네이트 수지, 폴리프탈아마이드 수지, 플리프탈이미드 수지 등 내열성과 기계적 강도가 높은 고가의 수지가 주로 사용되고 있으며 이들 수지의 사출온도는 200℃ 이상이다.The metal used here is mainly iron or copper or iron or copper plated with chromium, nickel, gold or silver.As plastics, heat resistance and mechanical properties such as polycarbonate resin, polyphthalamide resin, and polyphthalimide resin are used. Expensive resins with high strength are mainly used and the injection temperature of these resins is 200 ° C or higher.
여기에서 접착필름을 사용하는 이유는 사출되는 플라스틱과 금속간의 접착력을 좋게 하여주기 위한 것이다.The reason for using the adhesive film here is to improve the adhesion between the plastic and the metal to be injected.
접착필름의 원료로서는 상온에서 점탄성(粘憚性)을 갖는 다양한 종류의 합성수지가 사용될 수 있다.As a raw material of the adhesive film, various kinds of synthetic resins having viscoelasticity at room temperature may be used.
그러나 두께가 0.05~0.1㎜로 얇은 접착필름은 사출온도가 310℃ 정도인 폴리카보네이트와 같은 내열성이 높은 플라스틱의 사출온도에서 내열성을 유지하기가 어렵다는 문제가 있다.However, a thin adhesive film having a thickness of 0.05 to 0.1 mm has a problem in that it is difficult to maintain heat resistance at an injection temperature of a high heat resistant plastic such as polycarbonate having an injection temperature of about 310 ° C.
상기와 같이 금형(mold)내에서 금속과 플라스틱을 접착시켜주는 방식을 이 분야에서는 인몰드접착방식이라고 한다.As described above, the method of bonding the metal and the plastic in the mold is called in-mold bonding in this field.
종래 인몰드 접착방식으로 소형 전자제품의 하우징을 제조할 때는 금속판에 금속판의 형상과 동일하게 재단된 접착필름을 접착시킨 상태에서 이를 금형에 넣고 여기에 용융된 플라스틱을 사출하여 금속판과 플라스틱을 접착시켜 금속-플라스틱 복합재로 된 하우징을 제조하고 있다.When manufacturing a housing of a small electronic product by the conventional in-mold adhesive method, the adhesive film cut in the same shape as the shape of the metal plate is bonded to the metal plate, put it in a mold, and inject the molten plastic therein to bond the metal plate and the plastic. A housing is made of a metal-plastic composite.
폴리카보네이트 수지나 폴리프탈이미드 수지의 사출온도는 250~350℃이고 접착제의 용융온도는 200℃이하이므로 접착제가 부분연소되어 탄화되거나 흘러내리는 경향이 있어 금속-플라스틱간의 접착불량이 발생하는 경우가 많이 있고 또한 금속판이 평면이 아니고 굴곡면을 갖는 경우가 많아 필름상의 접착제를 금속판과 일치되도록 밀착시켜주는데 작업자의 수공(手工)이 많이 소요되므로 생산성이 떨어지는 문제가 있다.Since the injection temperature of polycarbonate resin or polyphthalimide resin is 250 ~ 350 ℃ and the melting temperature of adhesive is 200 ℃ or less, the adhesive is partially burned and tends to be carbonized or dripping, resulting in poor adhesion between metal and plastic. In many cases, the metal plate is not flat but has a curved surface, so that the adhesive on the film is brought into close contact with the metal plate, which requires a lot of manual labor for the worker, thereby reducing productivity.
본 발명의 목적은 금속-플라스틱 접착용 프라이머 조성물을 제공하는데 있 다.An object of the present invention is to provide a primer composition for metal-plastic adhesion.
본 발명자들은 인몰드 접착방식으로 금속과 플라스틱을 접착시켜주고자 할 때 종래 필름상 접착제 대신에 열가소성수지와 열경화성수지를 일정비율로 혼합하여서 조성시킨 프라이머 조성물을 금속표면에 도포한 후 금속과 플라스틱을 접착시켜주게 되면 필름상 접착제를 사용하지 않고도 간단한 공정으로 금속과 플라스틱을 견고하게 접착시켜줄 수 있는 것을 확인하고 본 발명을 완성하게 되었다.The present inventors applied a primer composition formed by mixing a thermoplastic resin and a thermosetting resin in a predetermined ratio instead of a conventional film adhesive when the metal and plastic are to be bonded by an in-mold adhesive method on a metal surface and then applying the metal and plastic. When gluing, it was confirmed that the metal and plastic can be firmly bonded in a simple process without using a film adhesive, and completed the present invention.
본 발명은 금속-플라스틱 접착용 프라이머 조성물에 관한 것이다.The present invention relates to a primer composition for metal-plastic adhesion.
구체적으로는 인몰드 접착방식으로 금속면에 용융합성수지를 접착시켜주는데 있어서 금속과 플라스틱간의 접착을 용이하게 하여 주기 위해서 금속표면에 도포하여 사용하는 프라이머 조성물에 관한 것이다.Specifically, the present invention relates to a primer composition applied to a metal surface in order to facilitate adhesion between a metal and a plastic in bonding a molten synthetic resin to a metal surface by an in-mold adhesive method.
어떤 물체에 도료(paint)를 도포하여 도장하거나 이종(二種)의 물체를 접착시켜줄 때 이종의 물체가 서로 용이하게 밀착되도록 하기 위해서 소량의 접착반응개시제를 물체에 도포한 후 도료 또는 접착제를 사용하는 경우가 있는데 이때 소량으로 사용되는 접착반응개시제를 이 분야에서는 전처리제 또는 프라이머라고 한다.In order to make the different kinds of objects adhere to each other easily when painting or painting by applying paint to a certain object, apply a small amount of adhesion initiator to the object and then use paint or adhesive. In this case, the adhesion initiator used in a small amount is called a pretreatment agent or a primer in this field.
이하 실시예를 들어 본발명을 구체적으로 설명한다.The present invention will be described in detail with reference to the following Examples.
실시예Example
<프라이머 조성물의 제조예><Production Example of Primer Composition>
실시예 1Example 1
본발명의 프라이머 조성물은 주재(主材)와 경화제(硬化劑)로 구성된 2액형 프라이머이다.The primer composition of this invention is a two-component primer comprised from a main material and a hardening | curing agent.
주재residence
① 에폭시수지(당량 850) 300g (19wt%)① Epoxy resin (equivalent to 850) 300g (19wt%)
② 메틸셀룰로오스 200g (12.5wt%)② Methyl Cellulose 200g (12.5wt%)
③ 폴리비닐아세테이트 200g (12.5wt%)③ Polyvinylacetate 200g (12.5wt%)
④ 메틸에틸케톤 400g (25wt%)④ Methyl ethyl ketone 400g (25wt%)
⑤ 톨루엔 400g (25wt%)⑤ 400g (25wt%) toluene
⑥ 멜라민수지 100g (6wt%)⑥ Melamine resin 100g (6wt%)
(애경화학제품 상품명 L-117-60) (Aekyung Chemical Product Name L-117-60)
상기 성분 중 반응기에 ④⑤를 투입하고 교반하면서 ②③을 천천히 투입하고 반응기 내부 온도를 60℃까지 올려서 3시간을 유지한 다음 내용물이 완전히 용해되었는지 확인 후 ①을 투입하여 다시 1시간 유지한 다음 30℃로 냉각하여 ⑥을 투입하고 15분 교반 후 300목 망사로 여과하면 약한 황색의 점주성 투명액체 1600g이 얻어진다.Put ④⑤ into the reactor of the above ingredients and slowly add ②③ while stirring and maintain the reactor temperature up to 60 ℃ for 3 hours, and then check whether the contents are completely dissolved. After cooling, ⑥ was added, stirred for 15 minutes, and filtered through 300-neck mesh to obtain 1600g of a weak yellow viscous transparent liquid.
본발명의 프라이머 조성물은 사용시 경화제를 첨가하여 사용하는 2액형 프라이머이다.The primer composition of the present invention is a two-component primer used by adding a curing agent in use.
상기에서 얻어진 주재에 사용되는 경화제로서는 이소시아네이트계 화합물인 디페닐메탄 디이소시아네이트(Diphenylmethane-4,4′-diisocyanate: 애경화학제품, 상품명 AK-75)를 사용한다.As a hardening | curing agent used for the main material obtained above, diphenylmethane diisocyanate (Diphenylmethane-4,4'-diisocyanate: Aekyung Chemical, brand name AK-75) which is an isocyanate type compound is used.
주재와 경화제의 사용비율은 주재 95~97wt%에 경화제 3~5wt%가 적당하다.The use ratio of the main material and the curing agent is suitable for the main material of 95 ~ 97wt% and 3 ~ 5wt% of the curing agent.
본발명은 열경화성수지 20~30wt%, 열가소성수지 20~30wt%, 용제 40~60wt%로 조성된 주재에 주재 95~97wt%에 대하여 경화제 3~5wt%를 첨가하여서 프라이머 조성물을 조성시키는데 그 특징이 있다.In the present invention, the primer composition is formed by adding 3 to 5 wt% of the curing agent to 95 to 97 wt% of the main ingredient, which is composed of 20 to 30 wt% of the thermosetting resin, 20 to 30 wt% of the thermoplastic resin, and 40 to 60 wt% of the solvent. have.
일반적으로 열가소성수지는 내열온도가 낮으며 플라스틱과의 접착력은 우수하나 금속과의 접착력이 좋지 않은 특성이 있다.In general, thermoplastic resins have a low heat resistance and excellent adhesion to plastics but poor adhesion to metals.
또한 열경화성수지는 내열온도가 높으며 열경화성수지나 금속과의 접착력은 우수하나 열가소성수지와는 접착력이 좋지 않은 특성이 있다.In addition, the thermosetting resin has a high heat resistance temperature and excellent adhesion to the thermosetting resin or metal, but has a poor adhesive strength with the thermoplastic resin.
본발명자들은 금속과 플라스틱을 접착시켜 주는데 있어서 열경화성수지나 열가소성수지를 일정비율로 혼합하여 조성된 프라이머를 사용하게 되면 열가소성수지만을 사용한 경우보다 높은 내열성을 유지하면서 금속과 플라스틱의 접착능력을 향상시켜줄 수 있을 것이라는 점에 착안하여 본발명을 완성하게 되었다.The present inventors can improve the adhesion between metal and plastic while maintaining a higher heat resistance than using a thermoplastic resin by using a primer formed by mixing a thermosetting resin or a thermoplastic resin at a predetermined ratio in bonding the metal and the plastic. The present invention was completed with the idea that it would be possible.
그러나 열경화성수지를 사용함에 따라 일정량의 경화제의 사용이 불가피하게 되어 사용시 주재에 경화제를 첨가하여 사용하여야 하는 2액형 프라이머로 구성시킨 것이다.However, as the thermosetting resin is used, the use of a certain amount of curing agent is inevitable, and it is composed of a two-component primer that must be used by adding a curing agent to the main material when used.
상기 실시예 1에서 에폭시수지와 멜라민수지는 열경화성수지이고, 메틸셀룰로오스와 폴리비닐아세테이트수지는 열가소성수지이고, 메틸에틸케톤과 톨루엔은 용제로 사용되는 것이다.In Example 1, the epoxy resin and the melamine resin are thermosetting resins, the methyl cellulose and polyvinylacetate resins are thermoplastic resins, and methyl ethyl ketone and toluene are used as solvents.
특히 에폭시수지와 우레탄수지는 금속과의 접착력이 우수한 특성이 있을 뿐만 아니라 내열성이 우수하여 프라이머 내열성을 높여준다. 셀룰로오스수지와 폴리에스테르수지는 플라스틱과의 접착력이 우수한 특성을 나타낸다.In particular, epoxy resins and urethane resins not only have excellent adhesion to metals but also have excellent heat resistance, thereby enhancing primer heat resistance. Cellulose resins and polyester resins exhibit excellent adhesion to plastics.
실시예 2Example 2
주재residence
① 에폭시수지(당량 850) 300g (19wt%)① Epoxy resin (equivalent to 850) 300g (19wt%)
② 열경화성우레탄수지 100g (6wt%)② Thermosetting urethane resin 100g (6wt%)
③ 니트로셀룰로오스(1/2초) 100g (6wt%)③ Nitrocellulose (1/2 second) 100g (6wt%)
④ 폴리에스텔 수지 300g (19wt%)④ 300g (19wt%) polyester resin
⑤ 메틸에틸케톤 400g (25wt%)⑤ Methyl ethyl ketone 400g (25wt%)
⑥ 톨루엔 400g (25wt%)⑥ Toluene 400g (25wt%)
상기 성분 중 반응기에 ⑤⑥을 투입하고 교반하면서 ③④를 천천히 투입하고 반응기 내부온도를 60℃까지 올려서 3시간을 유지한 다음 내용물이 완전히 용해되었는지 확인한 후 ①②투입하여 다시 1시간 유지한 다음 30℃로 냉각하여 300목 망사로 여과하여 약한 황색의 점주성 투명액체 1600g을 얻는다. 여기에 경화제로서 디페닐메탄디이소시아네이트(애경화학제품, 상품명 AK-75) 3.85wt%를 첨가하여 본발명의 프라이머 조성물을 얻었다.Of the above components, ⑤⑥ was added to the reactor while stirring, ③④ was slowly added, and the temperature inside the reactor was raised to 60 ℃ to maintain 3 hours, and then the contents were completely dissolved. The resultant was filtered through a 300-neck mesh to obtain 1600 g of a weak yellow viscous transparent liquid. 3.85 wt% of diphenylmethane diisocyanate (Aekyung Chemical, AK-75) was added as a curing agent to obtain a primer composition of the present invention.
비교예 1Comparative Example 1
인몰드 접착시 접착필름으로 사용되는 아크릴수지를 원료로 하는 열가소성의 아크릴수지계 프라이머를 준비하였다.A thermoplastic acrylic resin primer prepared from an acrylic resin used as an adhesive film for in-mold adhesion was used.
아크릴수지 300g (23wt%)Acrylic resin 300g (23wt%)
메틸에틸케톤 500g (38.5wt%)Methyl ethyl ketone 500g (38.5wt%)
톨루엔 500g (38.5wt%)Toluene 500g (38.5wt%)
상기 성분을 반응기에 투입하고 내부온도를 60℃까지 올려서 3시간 유지시켜 아크릴수지를 용제에 완전히 용해시켜 아크릴수지계 프라이머를 얻었다.The component was added to the reactor, the internal temperature was raised to 60 ° C. and maintained for 3 hours to completely dissolve the acrylic resin in a solvent to obtain an acrylic resin primer.
비교예 2Comparative Example 2
열경화성의 에폭시수지계 프라이머를 준비하였다.A thermosetting epoxy resin primer was prepared.
에폭시수지 500g (33.3wt%)Epoxy Resin 500g (33.3wt%)
메틸에틸케톤 500g (33.3wt%)Methyl ethyl ketone 500g (33.3wt%)
톨루엔 500g (33.3wt%)Toluene 500g (33.3wt%)
상기 성분을 반응기에 투입하고 내부온도를 60℃로 올려서 3시간 유지시켜 에폭시수지를 용제에 완전히 용해시켜 에폭시수지계 프라이머를 얻었다.The component was added to a reactor, the internal temperature was raised to 60 ° C., and maintained for 3 hours. The epoxy resin was completely dissolved in a solvent to obtain an epoxy resin primer.
<접착력시험><Adhesion test>
접착력시험 1
상기 실시예 1, 2 및 비교예 1, 2에서 얻은 프라이머 조성물을 몰드에 삽입할 금속(구리에 크롬도금)에 스프레이 방식으로 건조 후 도막 두께가 5㎛되도록 도포한 것을 각각 금형에 넣고 폴리카보네이트 수지를 사출온도 250~350℃에서 사출한 다음 실험한 것을 표 1에 나타냈다.The primer compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were dried on a metal (copper chromium plating) to be inserted into the mold by spraying, and then coated in a mold so that the coating thickness was 5 μm. Injected at an injection temperature of 250 ~ 350 ℃ it was shown in Table 1 the experiment.
[표 1]TABLE 1
변화없음=○, 경미한 변화=△, 심각한 변형으로 사용 불가=×No change = ○, slight change = △, not available due to severe deformation = ×
무처리금속 : 프라이머를 도포하지 않은 금속을 사용한 경우임.Untreated metal: When metal without primer is used.
상기 [표 1]에서 변화없음은 완전한 접착상태를 나타낸 것을 의미하고 경미한 변화는 사용가능한 접착상태를 나타낸 것이고, 심각한 변형은 사용 불가능한 접착상태를 나타낸 것임. No change in [Table 1] means a complete adhesion state and a slight change represents the usable adhesion state, a severe deformation represents the unusable adhesion state.
접착력시험 2
접착력시험 1과 동일한 방법으로 하되 다만 폴리카보네이트 수지를 폴리프탈아미이드 수지로 변경하여 사출온도 250~350℃에서 사출한 다음 실험한 것을 표 2 에 나타내었다.In the same manner as in the
[표 2] TABLE 2
변화없음=○, 경미한 변화=△, 심각한 변형으로 사용 불가=×No change = ○, slight change = △, not available due to severe deformation = ×
상기 표 1 및 표2를 관찰해보면 금형에 프라이머 처리를 하지 않은 금속을 넣고 폴리카보네이트 수지나 폴리프탈아마이드 수지로 압출 성형한 제품은 금속과의 접착이 불량하여 사용이 불가능하며 일반적으로 사용하는 열가소성의 아크릴수지계 프라이머는 사출시 흐름성이 나쁘고 열처리 과정에서 소실되거나 흘러내렸으며 또한 열경화성인 에폭시 프라이머는 충격실험에서 쉽게 박리되었다.Observing the Table 1 and Table 2, the product which is made of the non-primed metal in the mold and extruded with polycarbonate resin or polyphthalamide resin is not used because of poor adhesion with the metal, Acrylic resin primers had poor flowability during injection, lost or flowed during the heat treatment process, and thermosetting epoxy primers were easily peeled off in the impact test.
하지만 표 1과 표 2의 결과를 보면 실시예 1의 조성물과 실시예 2의 조성물을 도포한 금속물을 금형에 삽입하고 폴리카보네이트나 폴리프탈아마이드 등의 플라스틱 물을 압출 성형하면 성형 시에는 흘러내리지 않고 성형 후에 내 충격성이 강하며 열경화성 도료를 도장하고 100℃~140℃에서 30분~1시간 정도 열을 가한 후에도 충격에 강하며 내약품성이 뛰어난 조성물을 얻을 수 있음을 입증하였다.However, in the results of Table 1 and Table 2, when the metal material coated with the composition of Example 1 and the composition of Example 2 is inserted into a mold and the plastic water such as polycarbonate or polyphthalamide is extruded, it does not flow down during molding. After molding, the impact resistance was strong, and after coating the thermosetting paint and applying heat for 30 minutes to 1 hour at 100 ° C. to 140 ° C., it was proved that a composition resistant to impact and excellent in chemical resistance was obtained.
본 발명에 사용될 수 있는 수지로서는 열경화성인 에폭시 수지와 우레탄 수지와 열가소성 수지인 부틸셀룰로오스, 니트로셀룰로오스, 카르복실 메틸셀룰로오 스, 하이드록시 에틸셀룰로오스, 하이드록시 메틸셀룰로오스와 셀룰로오스 아세테이트 부티레이트가 이용될 수 있으며 폴리비닐경화제로는 사용직전에 주재에 혼합하여 사용하는 이소시아네이트계와 아민화합물이 사용되어 질 수 있다.As the resin which can be used in the present invention, thermosetting epoxy resins, urethane resins and thermoplastic resins such as butyl cellulose, nitrocellulose, carboxymethyl cellulose, hydroxy ethyl cellulose, hydroxy methyl cellulose and cellulose acetate butyrate can be used. As the polyvinyl hardener, isocyanate-based and amine compounds mixed with the main material immediately before use can be used.
점도 조절을 위해서 사용되는 용제로서는 톨루엔, 메틸에틸케톤, 부틸셀루솔브, 에틸아세테이트, 부틸아세테이트, 이소프로필알코올 등이 사용된다.Toluene, methyl ethyl ketone, butyl cellus solvate, ethyl acetate, butyl acetate, isopropyl alcohol, etc. are used as a solvent used for viscosity adjustment.
바람직한 구성비율은 열경화성 수지로서 에폭시 수지와 열경화성우레탄 수지 20~30중량%와 열가소성수지인 비닐수지와 셀룰로오스수지, 폴리에스텔 수지 20~30중량%와 메틸에틸케톤과 톨루엔등의 용제를 40~60중량% 비율로 혼합하여 얻은 주재 95~97wt%에 경화제 3~5wt% 범위로 구성시켜주는 것이 적당하다.The preferred composition ratio is 20 to 30% by weight of epoxy resin and thermosetting urethane resin, 20 to 30% by weight of thermoplastic resin, vinyl resin and cellulose resin, 20 to 30% by weight of polyester resin, and methyl ethyl ketone and toluene as a thermosetting resin. 95 ~ 97wt% of the main material obtained by mixing in% ratio is suitable to configure in the range of 3 ~ 5wt% curing agent.
본 발명의 조성물은 인몰드 방식으로 금속-플라스틱을 접착시켜줄 때 금속표면에 도포하여 금속-플라스틱간의 접착력이 우수한 성형물을 얻을 수 있는 효과가 있다.The composition of the present invention has an effect of obtaining a molded article having excellent adhesion between the metal and plastic when applied to the metal surface when the metal-plastic is bonded in an in-mold manner.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05104638A (en) * | 1991-10-16 | 1993-04-27 | Kanebo Nsc Ltd | Production of base material-resin material composite |
| JPH07124995A (en) * | 1993-09-07 | 1995-05-16 | Fujitsu Ltd | Preparation of box for electronic instrument |
| JP2003268340A (en) | 2002-03-19 | 2003-09-25 | Toyo Ink Mfg Co Ltd | Adhesive and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05104638A (en) * | 1991-10-16 | 1993-04-27 | Kanebo Nsc Ltd | Production of base material-resin material composite |
| JPH07124995A (en) * | 1993-09-07 | 1995-05-16 | Fujitsu Ltd | Preparation of box for electronic instrument |
| JP2003268340A (en) | 2002-03-19 | 2003-09-25 | Toyo Ink Mfg Co Ltd | Adhesive and its use |
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