TWI301098B - Durable layer composition for in-mold decoration - Google Patents

Description

1301098 IX. INSTRUCTIONS: RELATED APPLICATIONS This application is based on 35 USC 119 ((eight) 士μ.,nn 0 0 claims the application of the United States temporary mouth accounted for alpha smashing a June case 6th 〇 / 624,126 唬 优惠 。 。 。 。 。 。 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于The composition of the durability layer used in the prior art. [Prior Art] The zinc mold method in the background mold of the present invention involves the plastic material of the object and is shaped like a sputum. Shi Tian, the heated material in the main nuclear pocket (4) The item is decorated. Usually, in each of the mold cycles, the type of decoration or protection _ = or the strip is automatically or manually ▼ in the cavity, when the plastic material = charge = Feeding, and placing and forming an interface with the ink force therein.... When the hole is drawn, the hot material is formed on the surface of the article: the object is formed. The heat is transferred in the decorative material. And become a thing of the sea, and by the method of decoration in the mold The method of prayer mode, such as heat 1::: not:::: permanent parts. It or embossing, can be used for this, and retracting the mold. These methods can also be called modulo: two: (four) transfer state ^ τ In己 (in - m〇id labeling) or 1301098 疋拉内涂# (in~m〇ld c〇ating), 可 the transferable protective material may be called a kind of thermal transfer coating or Durable coating. ★ The decorative strip or strip usually comprises a carrier layer, a dislocation durable steep layer, an adhesive or tie-coat layer, and a decorative pattern (metal or ink). After the injection molding transfer, the carrier layer and the release layer are removed, leaving the τ the durability layer as the outermost layer. The «Hao durable layer is the necessary part of the decorative ribbon or strip' because It is used as a scratch-resistant, scratch-resistant or wear-resistant, and dkf-producing material, and the molded article. A layer of effective durability must meet certain standards. For example, it must be a non-stick or non-barrier coating that can be rolled up And subject to the subsequent image forming conditions. Second, during the process of the injection molding process, it must be consistently matched with the 3d shape of the molded article. In addition, an effective durability layer must be able to withstand high shear. Force and high temperature polymer melted in the injection molding process. Further, it must have excellent solvent resistance and abrasion resistance to protect the decorative image during use. U.S. Patent No. 5,795,527 No. 1 discloses an in-mold decoration method in which a protective layer conventionally used as a hard coat layer is formed of a mouth v or an electron beam curable resin. U.S. Patent No. 5,955,204 discloses a transfer material having a layer of UVi as a protective layer. The 耵V absorbing layer comprises an acrylic polymer in which a skeleton having uv absorbing properties is introduced onto the molecular chain. However, if these long-lasting 1301098 layers are completely solidified before casting, they tend to crack or show defects. If the bend of the tip tax or the step height of the steep mountain is an important feature of the molded object 'especially this example... a partial cure or under curing (under_ cured) #久层, usually for follow-up The processing steps are not sufficiently hard (for example, sputtering of metal decorative layers, or vapor deposition, and patterning) which is a very desirable feature for most applications).

U.S. Patent Nos. 5,993,588 and 6,527,898 disclose a protective layer which is partially cured by thermal energy and subsequent post-cure curing after the molding process. These references claim that the composition disclosed in it can represent an improvement in the protective layer and provide a modified

A protective layer that is resistant to abrasion and chemical resistance and that does not tend to crack on the special portion of the surface of the mold. However, this protective layer has certain drawbacks. First, the use of reactive hydroxyl groups to synthesize and purify highly acrylated polymers for thermal crosslinking is reported to be expensive and time consuming. The acrylated acrylic polymer must be synthesized by a two-step reaction to form an acrylic polymer backbone and grafting the acrylate functionality. During the second grafting step, a side reaction such as gelation may occur, and the synthesis procedure becomes more difficult to control, leaving the produced polymer with a limited shelf life (shelve) Life). In addition, in order to achieve a highly lustrous metallic decorative layer, the partially thermally cured durable layer preferably has a high heat distortion temperature and still has (1) at high speed. Highly photoreactive for UV post-cure to achieve 1301098 acceptable scratch resistance, solvent resistance, and degree, D-profile molds... and (2) for 3... sameness. Unfortunately, these requirements tend to be inconsistent. Therefore, the durability layer composition has a narrow process window (two private windows) for the most ideal metal deposition :: mold/post cure process. The durable/protective layer and the in-mold decorative enamel obtained from these methods tend to be very brittle and may exhibit defects such as cracks and dust particles during handling and transfer. Further, t, the heat curing of the portion of the durability layer composition in the production coater # becomes more difficult to control. The high speed cross-linking required for low cost manufacturing typically results in poor storage stability or Fs1 (green time) when the coating fluid is shorter green. It is highly desirable to achieve a high cross-linking speed in the applicator by using a more stable composition with a wider coating process window. SUMMARY OF THE INVENTION A first aspect of the invention relates to a composition useful for the formation of a durable layer for use in in-mold coating, decoration, or marking methods. The composition comprises (i) an amino crosslinking agent; (Η) a υν curable monomer or valence polymer having at least one functional group reactive with the gas-based crosslinking agent, (iii) an acidic catalyst And (iv) a photoinitiator. In the formation of the uranium layer of the present invention, the amino cross-linking agent is permeable to self-crosslinking, and cross-linked to the amino group through a 1301098 ^ g energy group on the UV curable monomer or oligomer. The reaction of the amino group on the agent forms a route. The formation of the network is done under acidic and heat-curing conditions. The network formed by thermal curing after the method of "Chengcheng t" can be further strengthened by UV curing of the UV curable monomer or oligomer. This post-UV exposure can effectively provide additional Cross-linking acts to form a consolidated interpenetration network as a highly durable protective layer for the molded article. The durable layer composition of this month may further include the following species or more kinds of binders, polyfunctional polymer polymers or oligomers reactive with the amino crosslinking agent Add a promoter or antioxidant. Further, the durability layer composition of the present invention may further comprise an additive such as a photoreceptor, an oxygen scavenger, a u V absorber or a light stabilizer, a lubricant, or a colorant. A second aspect of the invention relates to an in-mold decoration method for producing an article having the durability layer of the present invention. The first aspect of this month relates to a molded knee article having the durable layer of the present invention on its surface. A fourth aspect of the invention relates to a plastic article comprising the durable layer of the invention, and a layer of a metallic layer, and/or an ink layer. The present invention achieves the object of providing a durability layer for in-mold decoration, and has an excellent surface product f at a low cost (example, hardness, abrasion resistance, chemical resistance, and 埶 曰 曰 曰 gt ; x , H疋), and has a wider geometry. In addition, the durability layer of the present invention can also make the process window for the subsequent image 10 1301098 image forming step simpler and wider. The detailed description of the present invention is shown as an in-mold decorative ribbon or strip. The cross-sectional view 'includes a carrier> f 々ή hm body layer (15), a release layer (1:L), a durable f-layer (1 2 ), and a decorative pattern acoustic layer (i 4). (4) layer (1 3), and an adhesive in the in-mold decoration method, the object or the strip (10) is fed into the domain carrier layer (15)) to make the ^ The nuclear surface is in contact, as shown in Figure 2 +. Bands or strips can be in the "/,. ~ Cheng - the shape of the hope. The step ... is formed in a hot manner: the carrier (1 5 ), the detachment (1 1 ), and the adhesive (14) layer ' can be simplified by the method of the prior art. Both the ruthenium and the adhesive layer can be incorporated into the present invention. The layer (15) is usually a plastic film having a layer thickness of from 大 to 50, preferably from about 丄〇 to about 50 μm. Polypropylene), Poly(terephthalic acid) B: (PET), Polyethylhnaphthalate Mountain Ammonium ethyl ester is particularly preferred because of the ~U, -1 (PC) film, mechanical stability. The low-density, high-transparency, and heat-dissipating layer (1 1, γ, · α can cause the in-mold decorative strip-like object to be detached from the carrier layer, in such a manner that the durability layer can be made 〇l〇98 p _ layer (i 3) damage is minimized, and a complete automatic roll change transfer process can also be performed during the prayer month. This detachment: usually a layer of low surface tension coating, such as Prepared from the material of butterfly, stone, or dioxane, or a layer of highly smooth and non-transparent polyacrylate selected from the group consisting of melamine, a film such as ai or Sn Prepared from a material consisting of a group consisting of decyl acrylate, vinyl oxide, vinyl ether, allyl, vinyl, unsaturated poly, or a blend thereof. The release layer may comprise a polycondensate, a copolymer, a blend, or is selected from the group consisting of epoxides, polyurethanes, polyamidiamines, polyamines, melamines, glandular roads, benzophenone roads, a complex in a group of similar and similar. The release layer disclosed in US Serial No. 60/564, No. 18, filed on April 20, 2008, is also suitable, and the full content thereof will be used as a reference. Such a delamination composition includes an amine aldehyde concentrate, and a radical inhibitor or quener. Some carriers may have sufficient release characteristics to act as a release layer. The adhesive layer (14) is incorporated into the in-mold decorative strip or strip to provide an optimally adhesive decorative layer on the top surface of the molded article. The material of the adhesive layer, such as polyacrylic acid brewing, polyacrylic acid vinegar, polystyrene, polycarbonate, polyurethane, polyester, polyamide, epoxy resin, ethylene vinyl acetate copolymer 12 1301098 UVA), Hot material elastomer, or a combination thereof, or a complex. Particularly preferred are hot-melt or hot-lived lysines and polyamines. The thickness of the adhesive layer can range from two = about 20 microns, preferably about: as in the range of July 6th, 2002. July 2nd, 〇曰 Applying the beauty of the application No. 60/589,708 ♦ _ _, the letter of the order cited and ... a sensitive adhesive layer is also suitable, and this is used as a reference. Such adhesive shoulders and articles include a recording agent and a polymeric particulate material. The decorative layer (i 3 ) may be subjected to a method of mineral reduction, and thereafter, a metal layer or an ink layer formed by a (M) M emulsion phase deposition method or a μ ® ^ ^ patterning method. The ink pattern is slaughtered on a substrate layer, such as a gravure: (d). A similar method is used to form a similar one. The gravure fast drying, screen printing, sublimation heat conversion, or the mouth substrate layer may be a layer of jg 疋 layer plastic enamel layer, or a metal emulsifier box coated by an insulator, and made of carbon steel, stainless steel, A Bu, Ni, Cu,

Formed from Zn, Mg, or an alloy or oxide thereof. The decorative pattern can also be preformed by thermoforming. In the t sub-the carrier layer (15) will become the molded article 6:: piece. The decorative layer having a pattern of protrusions or depressions typically has a thickness in the range of from about 〇2 to about χ mm, preferably in the range of from about 〇3 to about 0.7. It is usually thermoformed from the legs of a mold (C-butyl-butadiene-styrene), polycarbonate, acrylic vinegar, polystyrene, or PVC sheets. In addition, the decorative layer can also be formed by pre-fabricating 13 1301098 by using Kelly molding, including the use of high-pressure air to create a decorative pattern on a film. The decorative layer can also be formed by hydroforming, wherein hydrostatic bladder (rather than air) is used as the forming mechanism. The durability layer (丄2) disclosed herein constitutes the present invention. The 痃 durability layer is formed of a composition comprising (i): an amino crosslinking agent; (ϋ) a U v curable having at least one functional group reactive with the amino crosslinking agent a monomer or oligomer; () a cerium catalyst; and (iv) a photoinitiator. The amino crosslinkers suitable for use in the present invention may include, but are not limited to, amine aldehyde concentrates, carboxyl modified amino resins, and other amino compounds. Examples of the amine S total concentrate include a formaldehyde concentrate of a polyfunctional amine (e.g., melamine or urea), such as melamine-formaldehyde, benzoguanamine monoaldehyde, glycoluril formaldehyde, or the like. The concentration of the amino cross-linking agent in the dried durability layer ranges from large, ', scoop 10 cc/ί> to about 8% by weight, preferably about 2 〇% by weight to about 60% by weight, And more preferably from about 4% by weight to about 5% by weight. Examples of commercially available amine acid concentrates may include Cytec products such as Cymel® (melamine), Melurac® (melamine) or Urac® (urea), and products from Surface Specialty UCB, such as Resimene ® (melamine-formaldehyde, HM or BM series of urea-formaldehyde, U series), Maprenal8 (melamine-methyl or abbreviated-formaldehyde), Viamin® (with alkyl or nitrocellulose tree 14 l3〇l〇98 months Highly reactive gland-formic acid) or M〇dae (tetra) 8 (highly reactive methylated melamine-methyl styrene modified styrene). The v v curable monomer or oligomer suitable for use in the present invention must have a reaction to the amino crosslinker and to a U V linkable functional group. The reaction can be carried out with an amino cross-linking agent, which can be a base, a sulfhydryl group, an amine, an amine, an amino acid, or the like, wherein the thiol and the slow base are Belongs to the better. The soil may be as follows: acrylate, methacrylic acid, allyl group, vinyl ether, epoxide, or a combination thereof, wherein cerium acrylate, methyl acrylate, or Thin scales are better. The equivalent weight of the functional group reactive with the amino crosslinking agent is preferably less than about 30 〇g//eq, more preferably less than about 2 〇 〇g/eq. The equivalent of the fluorene V crosslinkable functional group is preferably less than about 5 〇〇g/eg, more preferably less = about 20 〇 g/eq. The term "equivalent" is defined as the molecular weight of a single moon bean or an aroma polymer divided by the number of functional groups. The XJ V curable monomer or oligomer concentration in the dried durable layer ranges from about 10% by weight to about 60% by weight, preferably from about 20% by weight to about 5% by weight, and More preferably, it is about 2% by weight to about 40% by weight. Specific UV curable monomers or oligomers suitable for use in the benzene invention may include hydroxyalkyl acrylates, hydroxyalkyl methacrylates, hydroxy epoxides, carboxy acrylates, and carboxy methacrylates, Among them, 4 to hydroxybutyrate acrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate are more preferred. Soil 15 -Ϊ301098 % ^ The amino crosslinker used in the composition of the long-lasting layer and the U V curable monomer or polymer are bonded together to form a prepolymer. For example, the amino cross-linking agent can be reacted with the U V curable monomer or polymer at a high temperature in a reaction vessel to form the prepolymer. This reaction can be stopped before the gelation begins. The prepolymer is then used in the durability layer composition to accelerate the heat curing method. It should be understood that the scope of the present invention encompasses durable layer compositions (including amino crosslinkers and u V curable monomers or merging polymers as individual) and durable layer compositions (including amino crosslinks). The ligating agent is bonded to the uv-flavored mono- or valency I in the form of a prepolymer. In order to promote the thermal curing reaction, an acidic catalyst is required. P-toluenesulfinic acid is generally recommended for this purpose. The catalyst may be added with other ingredients, and may be present in an amount of from a large sum of the composition, from 0.5 to 5% by weight, preferably from about 1% by weight to about 3 weight%. Other acidic catalysts suitable for promoting thermal curing, may include inorganic acids, such as hydrochloric acid, or sulfuric acid; and organic acids, such as acid-filled derivatives; or many private sulfuric acid derivatives, such as DDBSA (dodecyl stupid) Sulfonic acid), and DNNDSA (dinonylnaphthalene disulfonic acid). In order to promote U V curing, the financial layer composition of the present invention also includes a photoinitiator (for example: 1, Type 2, and Type).

J-light initiator ' δ such as ITX from Ciba Specialty Chemicals

[Isopropyl thiophenidone oxime (3) substituted by Bu Chuan ^ "^ or ^ 々). The light initiator in the composition of 4, the total weight of the composition of 16 1301098 about 1% by weight to about 5 wt% is present at about 3% by weight. 鈥佺 is about 2 wt. / 〇 to the amino crosslinker, Τί catalyst, and photoinitiator or oligomer, acid 4 Han 7t initiator, The step-by-step includes the following points: the durability layer composition of the watch month can be smashed by the smashing knife or more species: the bond ~, -3⁄4 base parent agent reaction is sticky, and = brake Adhesion promoter, or anti-oxidation bismuth or oligomer, filler, medium, in: add a binder to the composition when i壬r plus, '表#王自口. Suitable binders can be packaged - not limited to cellulose derived exaggerated), rATW oxime 0 ^ such as CAB (acetic acid butyrate fiber ~ with, fortunate), hydroxypropyl cellulose (HPC), butyl butyl cellulose (HBC), K ethylcellulose (HEC), methylcellulose, 'MC), carboxymethylcellulose (CMC), carboxymethylacetate butyric acid, CMCAB, or copolymers thereof, Styrene-acrylic acid copolymer (-cryl p〇lymer), polyvinyl alcohol derivative, such as polyvinyl acetal vinylidene butyrate or its copolymer, or polymethyl methacrylate (PMMA) Preferred polymers include cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, polyvinyl ketamine, pMMA, and copolymers thereof. The binder in the composition may be present in an amount of from about 5% by weight to about 2,000% by weight based on the total weight of the composition, preferably from about 5% by weight to about 10% by weight. In another embodiment, the composition may further comprise a polyfunctional polymer or a merging polymer in order to increase the durability of the layer. 13 1301098 :. Read for this purpose 'the multifunctional polymerization The or the polymer must have a functional group (such as: mercapto, thiol, amine, guanamine, or urethane) that participates in the formation of the network through crosslinking. The amino-crosslinking agent can be modified to include the polymer or oligomer of this energy. For example, -97 is suspected of: a modified melamine containing about 2% stupid B: a propane' and the Resnnene 2040 is a modified melamine ~ 八 ^ '丨 containing about 4 Q% Styrene allyl alcohol. Alternatively, it is also possible to add a polyfunctional polymer or a polymer. Suitable polyfunctional poly, materials: may include, but are not limited to, hydroxyl-polyester resin, styrene~, :: alcohol copolymer polyol, acrylic polyol, and more than 35, of which polyol resin, benzene Ethylene allyl alcohol copolymer polyols, as well as acrylic polyols, are more preferred. Commercially available polyfunctional polymers or oligomers, which may include SAAO (stupid, succinyl alcohol copolymer polyol), Acryflow® (acrylic polyol), and Joncryl® (styrene-acrylic acid copolymer polyol) ). The polymer or polymer of the polymer may be present in an amount of from about 1% by weight to about 5% by weight based on the total weight of the composition, preferably from about 5% by weight to about 3% by weight. In still further embodiments, the composition may further comprise a filler to increase the hardness and abrasion resistance of the coating. Suitable fillers may include cerium oxide, CaC 〇 3, gel particles, or mica, particularly cerium oxide. The filler may be present from about 3% by weight to about 18 1301098 to about 20% by weight of the total weight of the composition, preferably %. D further % to about 10 weights In a further specific aspect, Bai Zhaoyi ## # y Μ,, and the composition can further include a kind of adhesion promoter. Appropriate spots $# ...m Tongtian's stick promoters may include (but are not limited to) esters of acrylic acid, eyebrows, and females. It is a propylene U, an organic chelate, an organic titanium i I, or a bismuth citrate, a titanium phosphate ^ ^ ^ ^ 乂 and a decane coupling agent, and the vinegar of the bismuth is more preferred. Examples of commercially available adhesion promoters are packaged as (10) coffee, (10) (6), and (10) as acrylic acid (qua), supplied by Sartomer). The 5H adhesion promoter may be present in an amount of from about 3% by weight to about 12% by weight based on the total weight of the ugly product, preferably from about 3% by weight to about 5% by weight. In a further step-by-step manner, an antioxidant such as: Cong [butyric acid toluene], face q [chlorinated quinone], or four [methylene- 3 (3, 3) can be added. 5, _di-tert-butyl _4_ via phenylmethane. The anti-oxidant may be present in an amount of from about 1% by weight to about 2% by weight based on the total weight of the composition, preferably about 〇·2% by weight. To a specific aspect of the weight %., the durable layer of the present invention may comprise an amino crosslinked roll, |, g 士 L ^ _ /, having at least a reaction with the gas-based crosslinking agent A "b-based u V curable monomer or oligomer, an acidic catalyst, a photoinitiator, and a selective antioxidant. In addition to the components of the 4X, Tingquan and its components, the composition may be more Further package 19 1301098 includes an additive such as a photoreceptor (eg, ITX); an oxygen scavenger (eg, diethylamine, diethanolamine, N-decyldiethanolamine, alkyl N,N-dimethylaminobenzoate, or 2,6-diisopropyl-n,N-diphenylaniline), UV absorber (for example, triazine, or benzotriazole derivative), or Stabilizer (for example: hindered amine light stabilizer), lubricant (for example: hydrazine acrylate, zinc stearate, or microcrystalline wax), or a coloring agent. 泫 Photoreceptor (if present) "Typical The concentration range may range from about 5% by weight to about 5% by weight of the total composition. The typical concentration range of the oxygen scavenger (if present) may range from about 丄% by weight to about 5% by weight of the total composition. The typical concentration range of the uv absorber, if present, may range from about 0.5% to about 4% by weight of the total composition. The typical concentration range of the light stabilizer (if present) is It is about 重量 by weight of the sum of the composition. /% by weight. The lubricant, if present, is typically concentrated and dry, and may be from about 5% by weight to a large amount of the total of the composition. & In forming the durability layer, four main components (1) are selected: such as J '(U) UV curable monomer or oligomer; (out) acidic catalyst; and (iv) photoinitiator, force , ( Multiple additives), disperse Ge, red selective ingredients and add eJ) knife or gluten solution in a suitable solvent, such as ketones, esters, ethers, glycolozolone, 1 κ(10) ·', buccal, ethyl-alcohol ether esters, quinones and esters, such as (Μί>Κ), cycloheximide, ethyl decyl acetate are preferred. 8 acid propyl ester, and acetic acid Butyl ester 20 1301098 In the formation of decorative ribbons or strips (1 ο) in the crucible, the layers f Ί Ί , 1 ), the durability layer ( 1 2 ), the decorative pattern layer ( 13), and the patch layer (/4) and the adhesive layer (14) are coated on the carrier layer (χ5). The coating can be made by a coating method, such as trench coating (_c〇atlng) ik_(d〇ct〇rbiadec〇ating) i coating, roller coating, blade coating ( C. Acoating, edge coating (lip eoatmg), and the like, or by printing methods such as gravure printing, screen printing, and the like. After forming the decorative ribbon or strip, the curing step of the durable layer is performed during the drying step of the coating, and the post-curing step is selectively performed after the coating. . The thermal cure can be carried out at various temperatures of from about 8 (TC to about 15 ±), for example from a few seconds to a few hours, depending on the curing conditions and the composition. The UV cure is in the process of injection. After the protective layer is transferred to the surface of the object of the prayer pattern, the molded article is placed on an ongoing UV conveyor, for example, ◦ 6 to 1 ft The required UV curing energy is usually in the range of from about 〇1 to about 5 J/cm 2 ', preferably from about 〇·3 to about " J/cm 2. The durability layer of the present invention is suitable for all of An in-mold decoration method for manufacturing a plastic article. Examples of materials suitable for the article may include, but are not limited to, thermoplastic materials such as polystyrene, polystyrene, acrylic acid, poly maple, and poly , polypropylene oxide, poly-smoke, propylene-butadiene-styrene-ethylene copolymer (ABS), methyl acetonate-acrylonitrile-butadiene-styrene copolymer (mabs), Polycarbon (4), polybutadiene 21 1301098: p-xylylene sm (PBT), polyterephthalic acid Ethylene _(ρΕτ), polyurethane, and other thermoplastic elastomers or blends thereof; and ' ''materials' such as reactive injection molding grade polyurethane, ring', ,, :: and polyester, Vinyl vinegar, or a composite thereof, prepreg 2: blending the article may be a plastic cover for a mobile phone or paper. In the case of I, the durable layer is suitable for any method of in-mold decoration: Plastic articles, such as personal accessories, toys or education I, a = digital assistant (pda) "electronic book" _book plastic cover, credit or smart card, identity card or name, thin cover, watch, watch : Machine or camera, car dashboard, household items, laptop external, = bag or any front panel of any consumer electronic device. The report is clearly listed. Other suitable plastic items for those skilled in the art It is obvious that 0 can be covered in the 'scope of the present invention: the durability layer of this bamboo shoot can also be applied to thermal transfer protective coatings for thermal printing, jet printing, and Passports and other identification applications. The present invention has been accomplished for the purpose of providing a durable layer or a protective coating for low cost, in-mold mounting with excellent surface quality, and a wide geometric tolerance to the right. The following examples are provided to provide a clear understanding and implementation of the present invention, which may be made by those skilled in the art. These embodiments should not be construed as limiting the scope of the invention with 22.1301098. Description and representative of the present invention.

Prepare an IMD tape with a durable layer between the release and adhesive layers - a solution of 102.8 grams, ie 5 1.4 grams of Cymel® / P 303 (2?? cyanamide resin 'from Cytec Industries Inc.) In 5 1.4 grams of MEK, 33.5 grams of 4-hydroxybutyl acrylate (from tCI), _ 10 grams of CAB-531-1 (cellulose acetate butyrate, from

Eastman Chemical Co.) was thoroughly mixed in a 90 gram MEK and mixed in a round bottom flask. The solution was heated to 80 C ' with stirring and 3 g of p-nonyl tartaric acid (from Aldrich) among 4.5 g of 2-propanol was added to the mixture. This solution was continuously stirred at 80 ° C for 2 〇 minutes and then cooled to room temperature. Finally, add 1.43 grams of BMS [4-(4-mercaptophenylphenylthio)-phenylindoleg, from Biddle Sawyer, Inc.], 0.76 _g of Irgacure 651 (2,2 - diterpene) Oxo-2-p-phenylacetophenone from Ciba Specialty Chemicals), 0.14 g of ITX (isopropyl thioxanthone from Biddle Sawyer, Inc.), and 0.095 g of Irganox 1035 (thiodivinyl- Bis(3,5-di(tert-)-butyl-tetra-p-phenylphenylpropionate octadecyl alcohol) from Ciba Specialty Chemicals), and 0.19 g of Tinuvin 123 [sebacic acid, bis(2,2, 6,6-Tetramethyl-1-(n-octyloxy)-tetracyridyl)ester, the reaction product of 1,1-didecylethyl hydroperoxide with octane, from 23 1301098

Ciba Specialty Chemicals, and 9 grams of mek, are added to the final solution. The durable layer composition was then coated on a commercially available release layer BOPP (biaxially oriented polypropylene from UCB Surface Specialties) using a #2 doctor blade. The coated composite film was air dried and cured for 5 minutes at 1 2 0 t:. ^ An adhesive consisting of 1 part of Sancure 2710 (aliphatic polyurethane) from Noveon Inc., Cleveland, OH, and 3 DI waters, using #1 6 Meyer rods, The adhesive is applied to the cured layer of durability to a target thickness of about 3 um. The final diaphragm was inserted into an injection mold. Then again on the 49th. F and 55〇. Under F, a mixture of PMMA (polymethyl methacrylate) and polycarbonate was inserted into a cavity where the adhesive layer was applied to the plastic mixture. After the release of the release layer, the durable layer and the adhesive layer are completely transferred to the molded plastic article. The molded article was then post-cured by U V exposure (1 J/cm2) using a Fusi〇n transport curing system. The solvent resistance and the abrasion resistance of the durability layer were estimated, and the results are summarized in Table 1. The solvent resistance of the samples was tested by a MEK titration test. The wear resistance was tested using a N0rman abrasion tester with a loading of 175 gm and a 5 〇 cycle. The pencil hardness was tested using a loading of 50 〇 gm. Example 2 A solution of 78.0 grams, i.e., 39. gram of Resimene 745 (melamine resin, from UCB Surface Special Hes, Inc.) in 39.0 grams of MEK, 20.0 grams of solution, is ι 〇〇 24 8 1301098 g of Acryflow A140 (acrylic polyol from Ly0ndell) in 10·0 g of MEK, 2 6 g of 4-hydroxybutyl acrylate (from TCI), 10·0 g of CAB~53 1 — 1 (cellulose acetate butyrate 'from Eastman Chemical Co.) in 90.0 grams of MEK, 10·0 grams of CD9052 (adhesion promoter from Sart〇mer), and 5 · 0 grams of solution' That is, 2 · 0 g of p-toluenesulfinic acid (from Aldrich) in 3 _ gram of 2-propanol, thoroughly mixed in a round bottom three-roller mill, lasting about 2 〇 Know. Further, 1·43 g of BMS, 0.76 g of Irgacure 651, 〇14 g of ITX, 0.1 g of Irganox 1035, and 0·19 g of Tinuvin 123, and 9 g of hydrazine were added to the mixture. The rest of the procedure is the same as in the examples, and the results are summarized in Table 1. Example 3 20.8 g of a solution, i.e., 10.4 g of Cymel M/F 303 in 10.4 g of MEK, 4.4 g of 4-hydroxybutyl acrylate, • 2·9 g of MEK-ST, 0.6 g CD9051 (trifunctional acid-based adhesion promoter from Sartomer), 0.6 gram Acryflow A140 in 〇6 gram MEK, 1.6 gram CAB-531-1 in 14.4 gram MEK, and A 2 gram solution, 0.8 g of p-nonyl sulfinic acid in 1.2 g of 2-propanol, was fully viscous. Add 0.29 grams of BMS, 〇·1 5 grams of Irgacure 65 1 , 0. 〇 3 grams of ITX, 0.02 grams of Irganox 1035, 〇·〇 38 grams of Tinuvin 123, and 1.8 grams of Μ ΕΚ to this mixture. . 25 1301098 The rest of the procedure is the same as in the examples' and the results are summarized in Table 1. Example 4 20.8 g of a solution, i.e., 10.4 g of Cymel 303 in 1 〇·4 g of MEK, 4.4 g of 4-hydroxybutyl acrylate, &lt; 2.9 g of MEK-ST, 0.8 g Acryflow A140 is contained in 0.8 g of MEK, 2.0 g of JPX-197T114-3 (styrene-acrylic acid copolymer from Joncryl polymer) in 8 g of MEK®, and 2 g of solution, ie It is 8 g of p-toluenesulfinic acid in 1 2 g of 2-propanol, and it is sufficiently mixed. Additional 〇.29 g of BMS, 0·15 g of Irgacure 651, 0·03 g of ITX, 0.02 g of irgan〇x 1035, 0.038 g of Tinuvin 123, and 1.8 g of MEK were added to the mixture. The rest of the procedure is the same as in the examples, and the results are summarized in Table 1. Example 5 A solution of 1 5.6 g, which is 7·8 g of Re si mene 745 in • 8.0 g of MEK, 10.2 g of CD570 (ethoxylated hydroxyethyl methacrylate), From Sartomer), 2 grams of CAB — 531 '-1 in 18 grams of MEK, 1 · 5 grams of solution, which is 〇. 6 λ gram of Ρ - toluene sulphate in 〇 · 9 grams Among the 2-propanol, mix thoroughly. An additional 0.29 grams of BMS, 0.15 grams of irgacure 651, 0·〇3 grams of 1TX, 0.02 grams of Irganox 1035, 0.038 grams of Tinuvin 123, and 1.8 grams of MEK were added to the mixture. The rest of the procedure is the same as in the examples, and the results are summarized in Table 1 for total 26 8 1301098. Example 6 (Comparative Example) A 76 gram solution of 38 grams of Resimene 745 in 38 grams of MEK, 1 gram of CAB-531-1 in 90 grams of MEK, and 5 grams of solution was used. The solution, which is 2 grams of p-indene. The acid is 'fully mixed in 3 grams of 2-propanol. Add 1.43 grams of BMS, 0.76 grams of Irgacure 651, 0.14 grams of ITX, 0.095 grams of Irganox 1035, 〇 19 grams of Tinuvin 123, %, and 9 grams of MEK to this mixture. The rest of the procedure is the same as in the examples, and the results are summarized in Table 1. Table 1 Example wrong pen hardness (500 grams) Anti-wear MEK resistance 1 &gt; 3H Excellent through 2 &gt; 3H Excellent through 3 &gt; 3H Excellent through 4 &gt; 3H Excellent through 5 &gt; 3H Preferably, by means of 6 (comparative) &gt; 3H, the invention, and the manner and method of making and using the invention, have been described in terms of 2, 1, clear, concise, and definitive terms, so as to be subordinate to this July. Anyone familiar with the technology can manufacture and use it. = </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; &amp; more specifically pointed out and clear please. The present invention is determined by the following patent scope. 27 1301098 [Simple Description of the Drawings] Fig. 1 is a cross-sectional view of an in-mold decorative strip or strip. Figure 2 shows that the in-mold decorative strip or strip is fed into a cavity. [Description of main component symbols] 1 0 · In-mold decorative tape or strip 1 1 · Release layer 1 2 · Durable layer 1 3 · Decorative pattern layer 1 4 · Adhesive layer 1 5 · Carrier layer

28

Claims (1)

1301098 X. Patent Application Range: A long-lasting layer composition for in-mold decoration, comprising: (i) an amino-crosslinking agent; (η)-having at least one functional group reactive with the amino crosslinking agent a UV curable monomer or polymer; w (丨i丨)-acid catalyst; and 1 (iv)-light initiator. 2) The durable layer composition according to claim 1 of the patent application, further comprising one or more of the following: (v) - a binder; (- having at least one multifunctional reactive with the amino crosslinking agent a polymer or a polymer; (vii) - a filler; (V111) - an adhesion promoter; or (ix) - an antioxidant. 3. a durable layer composition according to claim 1 of the patent application, The base-parent is an amine concentrate or a Wei-based modified amino tree. 4 The durable layer composition according to claim 1 of the scope of the patent application, wherein the secret concentrate is a polyfunctional amine (4) A shrinkage composition according to claim 4, wherein the polyfunctional amine is melamine or urea. The durable layer composition of the first aspect of the patent application, wherein the amino group is The crosslinking agent a-takes the melamine-formaldehyde, the benzoguanamine monoaldehyde, or the gannet 29 1301098 uric acid. 7 · The durable layer composition according to claim 1 of the patent scope, wherein the UV can be a functional group in a curing monomer or oligomer Is a hydroxyl group, a carboxyl group, a thiol group, an amine, a guanamine, or an amino phthalate. 8 · A durable layer composition according to claim 1 of the patent application, wherein the 忒u V curable monomer or oligomer A uv crosslinkable functional group is included which is selected from the group consisting of acrylates, methacrylates, allyl groups, vinyl ethers, epoxides, or combinations thereof. Ο 9 · According to The durable layer composition of claim 1, wherein the UV curable monomer or polymer is a hydroxyalkyl acrylate, a hydroxyalkyl methacrylate, a hydroxy epoxide, a carboxy acrylate, or Carboxy mercapto acrylate. 1 0 · Durable layer composition according to claim 1 of the patent application, wherein 3 ϋ V curable monomer or polymer is 4 butyl acrylate, hydroxyethyl Propyl acrylate or hydroxypropyl acrylate. 1 1 The durable layer composition according to claim 1, wherein the acidic catalyst is an inorganic or organic acidic catalyst. 1 2 · According to the scope of the patent application 1 1 durability layer composition, wherein The inorganic acid catalyst is hydrochloric acid or sulfuric acid. The chemically long-term layer composition according to claim 11 of the patent application, wherein the organic acid catalyst is p-toluenesulfinic acid, a phosphoric acid derivative, and a dodecapine group. Benzenesulfonic acid, or dinonylnaphthalene disulfonic acid. 1 4 · Durable layer composition according to item 1 of the patent application scope, Λ light initial agent is Norrish Type 1, Type 2, or Type 3 30 1301098 light Initiator. 1 5 . The durable layer composition according to claim 2, wherein the binder is a cellulose derivative or a copolymer thereof, a polyvinyl alcohol derivative or a copolymer thereof, or a polymethacrylic acid Methyl ester. 1 6 · a durable layer composition according to item 2 of the patent application scope, wherein the binder is cellulose acetate, cellulose acetate butyrate, cellulose acetate acetate, polyvinyl acetal, or poly Methyl methacrylate. The durable layer composition according to claim 2, wherein the polyfunctional polymer or oligomer comprises a functional group derived from a hydroxyl group, a carboxyl group, a thiol group, an amine group In the group consisting of guanamine, and carbamate. 18 According to the durable layer composition of the second item of the scope of the patent application, the eight-amino group and the double-linking agent are modified to contain a polyfunctional polymer or an oligomeric layer according to the second aspect of the patent application scope. A composition wherein the polyfunctional+ &amp; A/2 polymer/oligomer is a monohydroxy-polyester resin, a present ethylene-allyl alcohol copolymer polyol, an acrylic polyol, or a polyacid. · According to the scope of the patent, the long-term composition of the second paragraph of the patent scope, the total amount of the polymer or oligomer is a polyol resin, phenethyl alcohol copolymer polyol, Or acrylic polyol. Among them, 2 is the composition of the long-term layer of the second item of the patent scope, the organic chelate is the S-type of the propylene material, the metal (four) acid vinegar, the shixi burning organic titanate, or the acid salt, the mechanical titanium The compound, or 31 1301098 苴1 is a durable layer composition according to item 2 of the patent application scope, and the X standing accelerator is an ester of acrylic acid. Bean f 2 3 · According to the durability layer composition of the second application of the patent scope, the true filling system is cerium oxide, CaC03, gel particles, or mica.苴f = Durable layer composition according to item 2 of the patent application scope. 1. Tenghai antioxidant is butylated toluene, hydroquinone, or hydrazine. , 4, di-tert-butyl _4 _ hydroxyphenyl) propionic acid] A. Ο 2 5 The durable layer composition according to claim 2, which comprises an amino crosslinking agent, —At , a UV curable monomer or a polymer having at least one reactive soil with the amino crosslinking agent An acidic catalyst, a photoinitiator, and an antioxidant. 26. The durable layer composition according to claim 25 of the patent application, = one step comprising a polyfunctional polymer or oligomer reactive with the amino crosslinking agent. 2 7 · According to the patent application scope, the durability layer composition of the younger brother J b, further including a binder. It consists of a 32 1 8 · Durable layer composition according to the patent application 9 9 9 "Monthly No. 巳 巳 巳 巳 巳 , , , , , , , , , , , , , , 2 2 2 2 2 2 2 2 2 2 2 2 The durability layer of the in-mold decoration comprises the following composition: 3 (i) an amino crosslinking agent; 4 (η) * a UV curable monomer having at least one functional group reactive with the amino crosslinking agent or Oligomer; 1301098 (-acid catalyst; (ιν) a photoinitiator, and one or more of the following s: 、, 口, 与, with the amino a reactive polyfunctional polymer or oligomer, /, hydrazine, station promoter, or an antioxidant. 3 〇 · A plastic with a durable layer is printed by a sputum The following compositions are formed: (1) an amino-crosslinking agent; : b) * having at least one functional group-reactive Uv-curable monomer or polymer with the amino-crosslinking agent; (iii) An acidic catalyst; (lv) - a photoinitiator, and a binder, crosslinked with the amino group A material, an adhesion promoter, a polyfunctional polymer or oligomer reactive with one or more of the following optional agents, or an antioxidant. 3 1 · According to the scope of claim 3, which is a mobile phone Or plastic cover of paper, personal accessories, toys or educational skirts, personal digital assistant (PDA) e-book (e_b〇〇k) plastic cover, credit card or smart card, identity card or name #, thin cover, watch , front-end control panels for watches, radios or cameras, car dashboards, household items, laptop cases, tote bags or any consumer electronic device, and thermal transfer protective coatings for identity cards, passports, jet prints, or thermal print images 3 2 · A decorative strip or strip for in-mold decoration, the strip or strip comprising: a) a layer of carrier layer; 33 1301098 b) - layer of release layer; a layer of a durable layer formed of a composition comprising: (i) an amino crosslinker; (ii) a UV curable monomer or oligomer having at least one functional group reactive with the gas-based crosslinker (iii) an acidic catalyst; (iv) a photoinitiator, and one or more of the following optional binders, a polyfunctional polymer or oligomer reactive with the amino hexavalent agent, Filler, adhesion promoting or ~ antioxidant; training, d) a layer of decorative layer; and e) a layer of adhesive. 3 3 · decorative ribbon or strip according to item 32 of the patent application 'The decorative layer is a metal layer or an ink layer. 豢11, circle type: as the next page 34 1301098 4 VII. Designated representative map: (1) The representative representative figure of this case is: (1). (2) A brief description of the symbol of the representative figure: 1 0 · In-mold decorative strip or strip 11 · Release layer 1 2 · Durable layer, 1 3 · Decorative pattern layer φ 1 4 · Adhesive layer 15·Carrier layer 1 6 · Molding six or eight. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: