TW200417474A - Adhesive agent, process for manufacturing the same and plastic film laminated steel plate - Google Patents

Abstract

The purpose of the present invention is to provide an adhesive which shows excellent heat resistance after lamination processing and excellent adhesion after boiling water test, its manufacturing method and a plastic film laminated steel plate. The invented adhesive comprises (1) a polyester-polyurethane (A) with block isocyanate, which is produced by reacting a blocking agent with the unreacted isocyanate of an isocyanate containing polyester-polyurethane (A'), which is produced by reacting a polyisocyanate compound (Q) with a hydroxyl containing compound composition (P) containing polyester polyol (p1) and hydroxyl containing polysiloxane in a excessive isocyanate condition; (2) an epoxy resin (B); and (3) acid modified polyolefin resin. The invented manufacturing method is to mix the above-mentioned polyurethane (A), epoxy resin (B) and acid modified polyolefin (C) The invented plastic film laminated steel plate is manufactured by using the above-mentioned adhesive.

Description

200417474 • / 玖 Description of the invention: [Technical field to which the invention belongs] The present invention relates to an adhesive, a method for manufacturing the above adhesive, and a plastic film laminated steel plate. If the adhesive of the present invention is used, a laminate (1 a in i n a t e) of a plastic thin film and a steel plate can be obtained. [Previous technology] Laminated steel plates obtained by bonding plastic films with printed or knurled surfaces to steel plates are used in housings for home appliances and interior and exterior decoration building materials for houses. Compared with conventional metal decorations, It can be used as a material that improves design performance and high sense of touch. These laminated steel plates are generally manufactured by applying an adhesive to a steel plate and attaching a plastic film. As a material for this plastic film, for example, polyethylene gas has been widely and widely used for a long time. However, it is well known that polyethylene contains gas and has become an environmental issue. In addition, as an alternative material having the same performance as the polyethylene laminated steel sheet, a laminated steel sheet using a polyolefin film is known. As adhesives conventionally used when laminating a polyethylene gas film on a steel sheet, for example, epoxy resins and amine-based adhesives, or polyester polyols and polyisocyanate resin-based adhesives are known. Phase type. When these adhesives are used to laminate a polyethylene gas film on a steel sheet, the required physical properties are generally achieved. However, since a polyolefin film is a material that is difficult to adhere, if the above-mentioned adhesive for laminating a gas-gas baking film is also used, it will cause a problem of poor adhesion. As such an adhesive for a synthetic resin film and a metal material, 3 12 / Invention is called 补 (Supplement) / 93-03 / 92 丨 37437 200417474 A combination of a polys purpose polyol and a polyisoitic acid purpose compound is known. Into the composition. However, since this adhesive is generally a two-liquid phase, its operability is poor, and it is necessary to cure it after adhesion. In addition, a one-liquid type adhesive using a block polyisocyanate is also known, but because of its poor curability, it is necessary to perform heat treatment for a long time. In order to overcome the above-mentioned drawbacks, Japanese Patent Laid-Open No. 1 1-16 6 16 (Patent Document 1) describes an adhesive obtained by adding a phosphoric acid-modified epoxy resin. However, when laminating a polyolefin film on a steel sheet using the adhesive described in the above publication, it is difficult to ensure heat resistance after processing the laminate and adhesion after boiling water resistance test, etc. Adhesives for olefin laminated steel sheets include, for example, Japanese Patent Laid-Open No. 9-1 7 3 3 (Patent Document 2), Japanese Patent Laid-Open No. 9-3 0 9 1 7 7 (Patent Document 3), or Japanese Patent Laid-Open No. 1 0-4 4 3 1 2 (Patent Document 4). An adhesive containing a polyolefin resin modified with maleic anhydride or the like is described. That is to say, in each of the above-mentioned publications (Patent Documents 2 to 4), techniques for improving the adhesion between a polyolefin film and a steel sheet by adding an acid-modified polyolefin resin to a polyester resin, an epoxy resin, or the like are described. . However, even with these techniques, it is difficult to ensure the heat resistance after lamination of a polyolefin film on a steel sheet and the adhesion after a boiling water resistance test. <Patent Document 1 &gt; Japanese Patent Laid-Open Publication No. 1 1-1 6 6 1 6 6; <Patent Document 2 &gt; Japanese Patent Laid-Open Publication No. 9-1 7 3¾; &lt; Patent Literature 3 &gt; 6 312 / Invention specification (Supplement) / 93-03 / 92137437 200417474 Japanese Patent Laid-open No. 9-3 0 9 1 7 7; <Patent Document 4> Japanese Patent Laid-open No. 10-4 4 3 1 2. [Summary of the Invention] (Problems to be Solved by the Invention) Therefore, the problem of the present invention is to provide an adhesive, a method for manufacturing the adhesive, and a plastic film laminated steel sheet manufactured by using the adhesive, especially when laminated on a steel sheet. In the case of difficult-to-adhesive resin films such as polyolefin films, they exhibit excellent heat resistance after lamination, and at the same time, they can ensure excellent adhesion even after water-repellent experiments. (Means for Solving the Problems) According to the present invention, the above problems can be solved by the following adhesive, which is characterized by containing: (1) a polyester polyurethane (A) containing a block isocyanate group, The blocking agent will have an isocyanate group in excess of the total hydroxyl groups of the radical-containing compound component (P) including the polyester polyol (p 1) and the hydroxyl-containing polysiloxane compound (p 2), Unreacted isocyanate groups in the isocyanate group-containing polyester polyurethane (A ') obtained by reacting the above-mentioned hydroxyl-containing compound component (P) with the polyisocyanate compound (Q) are obtained by agglomerating; (2) epoxy resin (B); and (3) acid-modified polyroasting resin (C). In addition, the present invention also relates to a method for producing an adhesive, characterized in that it contains a component containing a radical group with respect to a poly (S1) polyol (p 1) and a hydroxyl-containing polysiloxane (p 2). (P) Total warp group, isocyanate group 3 丨 2 / Invention specification (Supplement) / 93-03 / 92 丨 37437 200417474: ,, / Under the condition of excess, the above-mentioned hydroxyl-containing compound component (P) and the poly compound (Q) reaction to prepare an isocyanate group-containing polyester poly (A ′), and then use a blocking agent to block the unreacted isocyanate groups in the isocyanate group-containing polyester ester (A ′) to prepare a block ester group-containing The polyester polyurethane (A) is then mixed with the polyester polyurethane (A) containing the block group, the epoxy resin (B), and the acid modification (C). The present invention also relates to a plastic film laminated steel plate characterized in that the plastic film and the steel plate are laminated by the above-mentioned adhesive. [Embodiment] The adhesive of the present invention contains a block isocyanate polyester poly &gt; (A). The above-mentioned block isocyanate polyester polyurethane (A) is a polyisocyanate compound (Q) which reacts with a polyisocyanate compound (Q) (under an excessive amount of conditions) to prepare an isocyanate-containing polyester ester (A ' ), And then using an agglomerating agent to block the obtained unreacted isocyanate groups in the isocyanate-containing amino ester (A ′) to produce the above-mentioned hydroxyl-containing compound component (P) containing a polyester polyol (P-based polysiloxane) The compound (P 2) is an essential component. The polyester polyol (ρ 1) is a main component that imparts flexibility to the adhesive of the present invention. The poly (S 1) polyhydric alcohol (ρ 1) is composed of a known polybasic acid and a polyhydric alcohol. The obtained thermoplastic resin can be used as a branched saturated thermoplastic resin or a thermoplastic resin, but the linear saturated type is better because the viscosity of the branched saturated type is excessively increased. 312 / Invention Specification (Supplement) / 93-03 / 92137437 Isocyanate amine polyimide polyisocyanate acidified isocyanate polyene resin, polyisocyanate-containing polycyanuric acid-containing polyamine polyamino acid (poly oligo-polyethylene glycol) containing hydroxycyanate group and polyhydroxy acid containing hydroxycyanate When linearity and saturation of the polyhydric alcohol condensation are linear, there may be no specific limit to the above-mentioned polyester polyvalent average molecular weight (Μη) as long as it can be dissolved in the solvent used, preferably 3,0 0 0, more It is preferably 10, 0 0 0 to 2 8, 0 0 0, and most preferably 2 3, 0 0 0. When the number of the polyester polyols (p 1) is equal to 8,0 0 0, the adhesive strength becomes weak, and for example, it peels when it comes into contact with hot water. On the other hand, when the number average molecular weight exceeds 30,000, the solubility is lowered and the viscosity of the adhesive is increased, so the state is difficult (the state where the solid content of the resin is increased). The glass transition temperature (T g) of the polyester polyol (p 1) is not limited, but is preferably 50 to 100 ° C., and more preferably 65 to 85 ° C. If the shift temperature is lower than 50 ° C, the heat resistance is insufficient. If it exceeds 10 [, the film becomes too hard, which may affect the processability. The glass transition temperature is appropriately selected and adjusted by using a polybasic acid and a polyol as raw materials. Two or more polyesters having different glass transition temperatures may be used to adjust the glass transition temperature to an appropriate glass transition temperature. As long as the hydroxyl-containing compound component (P) and polyisocyanate (Q) can be reacted under the condition that the isocyanate group is excessive, there is no specific limitation on the hydroxyl value of the alcohol (P1), and in the case of linear saturated fats In the following description, the hydroxyl value is preferably 20 mg KOH / g or less and 10 η gKOH / g or less. When the above-mentioned base value exceeds 20 ngKOH / g, the crosslinking is insufficient, and the viscosity becomes very high. The above-mentioned hydroxyl value is not particularly limited, but it is preferably 2 mgKOH / g or more, and more preferably. If the above-mentioned hydroxyl value is lower than 2 mgKOH / g, the reactivity with isocyanide (Q) is insufficient, and the adhesive force is insufficient. Excellent base value of 3 12 / Invention specification (Supplement) / 93-03 / 92137437 Alcohol (p 1) 8, 0 0 0 to 1 6, 0 0 0 to 1 I1 is easy to be in the solvent under the condition To achieve the specific fruit glass rotation to 1 ° C, the coating degree can be passed. In addition, the polyhydric alcohol (p 1) S is a polyester multi-component thermoplastic tree. More preferably, the lower limit of the coating film is 4 in g K 0 H / g. The range of the ester compound is 9 200417474/5 to 6 in. g Κ ◦ Η / g, within this range, can obtain excellent physical properties in terms of viscosity, crosslinkability and strength of the coating film. The acid value of the polyester polyol (p 1) is not particularly limited, but in order to suppress the reaction with the isocyanate compound (Q), it is preferably 7 in g κ 0 H / g or less, more preferably 4 丨 丨 丨g Κ 0 Η / g or less. If the acid value exceeds 7 丨 丨 丨 g K 0 Π / g, a foaming reaction occurs with the isocyanate, hindering the reaction between the isocyanate and the hydroxyl group. As the polybasic acid that can be used to prepare the polyester polyol (p 1), aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and biphenyl-1] , P'-dipic acid or biphenyl m, in'-dipic acid, or a monthly aliphatic polybasic acid, such as succinic acid, adipic acid, azelaic acid, sebacic acid, or dodecanedioic acid. Examples of the poly SI that can be used to prepare the polyester polyol (P 1) include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene, 1,4-butanediol, and 1 , 3-butanediol, neopentyl glycol, pentamidylene glycol, hexamethylene glycol, heptylene glycol or octaylene glycol. The polyacetic acid polyol (p 1) can be prepared by, for example, polycondensing the above-mentioned polybasic acid and polyhydric alcohol at 2000 to 250 ° C. A commercially available product can also be used as the polyester polyol (p 1), and specific examples thereof include VYL 0 NGK 6 4 0 (M η 218, 0 0 0, T g = 79. C, hydroxyl value = 5, acid value &lt; 4, linear type), VYL 0 NGK 8 8 0 (Μ η 28, 0 0 0, T g 28 8 0 0 C, hydroxyl value = 5, acid value &lt; 4, linear type ), VYL 0 N 3 0 0 (Μ η = 2 3, 0 0 0, T g 2 7. C, hydroxyl value = 5, acid value &lt; 2, linear,), VYL 0 N 5 0 0 (Μ η = 2 3, 0 0 0, T g = 4 ° C, hydroxyl value = 5, acid value &lt; 2, linear), VYL 0 N 5 6 0 (Μ η = 1 9, 0 0 0, T g = 7 ° C, 10 3 12 / hair lock instructions ||: 丨 K supplement) / 93-03 / 92 丨 37437 200417474 / hydroxyl value two 8, acid value &lt; 2, branch type), or VYL 0 N 6 3 0 (Μ η 2 2 0, 0 0 0, Ί 'g 2 7 5 ° C, hydroxyl value 2 5, acid value = 1, linear type) [above manufactured by Toyobo (share)]; or U Ε- 3 6 0 0 (Μ η 2 20, 0 0 0, T g 7.5 ° C, hydroxyl value = 4, acid value M) or UE-3 6 9 0 (Μ η 2 1 4, 0 0 0, T g = 9 1 ° C, hydroxyl value = 8, Value = 1) [more U N ITI K A (shares) manufactured by]. Particularly preferred commercially available products are VYL 0 NGK 6 4 0 or VYL 0 NGK 8 8 0. Polyol polyols that can be dissolved in methyl ethyl ketone (M EK) can also be used as appropriate, and VYL 0 NGK 6 4 0 or VYL 〇N GK 880 Substances with equivalent properties. As described above, the aforementioned radical-containing compound component (P) contains a hydroxyl-containing oxygen transfer compound (ρ 2) as an essential component. The hydroxy-containing polysiloxane (ρ 2) has a function of improving the heat resistance of the adhesive layer obtained by the adhesive of the present invention. The hydroxyl-containing polysiloxane (P 2) that can be used in the present invention can be any liquid or solid at normal temperature (for example, 25 ° C.), preferably a hydroxyl-containing polysiloxane that is solid at 25 ° C. Polysiloxane. In addition, compared with solid polysiloxanes, liquid hydroxy-containing polysiloxanes that are liquid at 25 ° C. may react with isocyanates even if the liquid polyoxygenates in the adhesive react with isocyanates. Part of the polysiloxane floats on the surface of the adhesive and prevents adhesion to the film. However, when a solid polysiloxane is used, excellent heat resistance can be obtained. The hydroxyl value of the hydroxyl-containing polysiloxane (ρ 2), which is solid at 2 5 ϋ C, is not particularly limited, but is preferably 300 mg κ 0 H / g · or less, more preferably 10 0 to 2 0 0 in g K 0 H / g. If the warp base value exceeds 300 nig K 0 H / g, the adhesion to the plastic film is poor, and if it is less than 1 0 nig K 0 H / g, the thermal properties are not good. In addition,

II 3 12 / Explanation of the invention 逬 (Supplement) / 93-03 / 92 丨 37437 200417474 ... / There is no specific softening point of the hydroxyl-containing polysiloxane (p 2) which is solid at 25 ° C IU system, preferably 40 ~ 1 0 (Γ C, more preferably 60 ~ 80 ° C. If the softening point is lower than 40 ° C, sometimes it is not solid but becomes liquid. If it exceeds 100 ° C, the coating film becomes too hard, and the processability is poor. As a hydroxyl-containing polysiloxane (p 2) that is solid at 25 ° C, a commercially available product can be used, and specifically 1 (R-2) 6 is preferred [Made by Shin-Etsu Chemical Industry Co., Ltd., Softening point = 7 5 ° C]. Compounds having the same characteristic values as the above KR-2 1 6 can also be appropriately used. The above-mentioned hydroxyl-containing compound component (P), except for the above-mentioned polyester In addition to the polyol (P 1) and the aforesaid polymer containing poly (oxygenated compound) (P 2), it may further contain a hydroxyl-containing epoxy resin (P 3) according to the situation. When using a hydroxyl-containing epoxy resin In the case of (P 3), the adhesiveness of the adhesive of the present invention can be improved. Examples of the hydroxyl group-containing epoxy resin (P 3) include a bisphenol A type epoxy resin. / Or bisphenol F-type epoxy resin, especially bisphenol A-type epoxy resin is suitable. In addition, the epoxy resin which is liquid at room temperature (for example, 25 ° C) is preferred. Use a liquid ring When a fluorene resin [for example, EPIK 0 TE 8 2 8] is used as the hydroxyl-containing epoxy resin (p 3), its hydroxyl group can be reacted with the isocyanate group of the polyisocyanate compound (Q). However, if a solid epoxy resin [for example, EPIK is used 0 ΐ E] 0 0 1] As a hydroxyl-containing epoxy resin (P 3), gelation occurs when reacting with a polyisocyanate compound (Q), making the reaction difficult. The above-mentioned hydroxyl-containing epoxy resin (ρ 3 The number-average molecular weight of) is not specifically defined. It is preferably 2 0 0 to 2, 0 0 0, more preferably 2 0 0 to 1, 5 0 0, and most preferably 2 5 0 to 1, 0 0 0. .If the number average is more than 2, 0 0 0, the coating film may become hard, resulting in poor processing. 12 3 丨 2 / Explanation of the gown (Supplement) / 93-03 / 92 丨 37437 200417474- / / / As the above-mentioned hydroxyl-containing epoxy resin (1) 3), the marketable products can include EPIK 0 TE 1 0 0 1. Manufactured by air resin (stock)], Λ RALDI Τ Λ ER 2 6 0 0 is converted into epoxy (strand), etc.] Among the above-mentioned hydroxyl-containing compound component (P), and the above-mentioned hydroxyl-containing polysiloxane compound (ρ 2) weighs 97/3 to 99.5 / 0.5, A suitable coating film performance (for example, heat resistance) of 98.5 / 1.5 to weight ratio (ρ 1 / ρ 2) of 9 7/3 to 9 9/5 / 0.5 is more preferable. However, when the above-mentioned hydroxy-containing polysiloxane in the compound component (P) is 0.5% by weight, heat resistance may be deteriorated, and if the amount of the compound (P2) exceeds 3% by weight, it may sometimes be reduced. In addition, in In the case of the above-mentioned hydroxy-containing compound component (j alcohol (ρ 1) and the above-mentioned hydroxy-containing polysiloxane (ρ epoxy resin (P 3)), their weight is 3/97 to 8/92, more preferably 5 / 95 ~ 7/93. The ratio of resin (P 3) exceeds 8 weight! Id, sometimes it is good, and 1 of the above-mentioned hydroxyl-containing epoxy resin (ρ 3) may have poor contact with steel plates. In the present invention In the above, as the hydroxyl-containing poly and cyanate ester compound CQ) ', any of the polyisocyanates prepared by using a polyester compound can be used. In particular, a triol (for example, Sanjing 曱 3 12 / 发 丨!)] Explanation β: (Supplement V93-03 / 92 丨 37437 Use commercially available products. As EP1K0ΤΕ 828 [Japanese ring or AR Λ LD 1 T 6 0 2 1 [Asahi polyester polyol (P 1 ) Amount ratio (ρ 1 / ρ 2), preferably 99.5 / 0.5 ° If it is within the above range, it is possible to obtain 'if the above-mentioned radical-containing compound is contained The amount of (ρ 2) is insufficient due to the above-mentioned hydroxyl-containing polysiloxane coating film being too hard, and the processability 3) in addition to the above-mentioned polyester poly 2), also contains a warp-based ratio [ρ 3 / (ρ 1 + ρ 2)] When the adhesion between the above-mentioned hydroxyl-containing epoxy and the steel sheet is less than 3% by weight, it is preferable to add a diisocyanate compound to the hydric alcohol reacted with the compound component (P). As a polypropane) or four Alcohols (Example 13 200417474 * &quot; \ / such as Lithyltetraol), etc. In addition, as the above-mentioned isocyanate added to a polyol, a well-known aromatic isocyanate compound, an aliphatic isocyanate, and / Or an alicyclic isocyanate compound. From the standpoint of excellent discoloration and non-coloring in terms of hygienic properties, an aliphatic or alicyclic isocyanate is preferred. Examples of the aliphatic isocyanate compound include hexamethylene sulfonate and isoisocyanate. Propyl diisocyanate, fluorenylene diisocyanate, hexamethylene diisocyanate, or benzene difluorenyl diisocyanate, etc. Also for the a-cyclic cyclic isocyanate compounds, isophorone diacetate, fluorenyl cyclohexane Diisocyanate, Amino acid diisocyanate or -1, 4-diisocyanate, etc. Examples of the aromatic isocyanate include fluorenylbenzylidene diisocyanate, 1,5-naphthylene diisocyanate, 4, 4, 4-diphenyl Pinane, diisocyanate, 4, 4, -diphenyldioxane diisocyanate, 4,4'-dibenzyl diisocyanate, tetraalkyldioxane isocyanate, dialkyldiphenyloxane diisocyanate, 1, 3'-based diisocyanate or 1,4'-phenylene diisocyanate, etc. Among them, the isocyanate compounds have excellent physical properties, but due to toxicity, it is necessary to pay attention to hygienic work. The polyisocyanate compound (Q) is preferably an isocyanurate as an isocyanate trimer from the viewpoint of heat resistance and the like. From the viewpoints of heat resistance and the like, particularly preferred is a trimer of hexamethylene diisocyanate 6!... As the polyisocyanate compound (Q), II products are also available. Specific examples include ΐ Λ Κ Ε Ν Α ΐ ED-1 7 0 N (Solid 3 丨 2 / Instructions of the Inventory of Zhouzhou) / 93-03 / 92 丨 37437 compounds, esters of 4 and non-esterified diisocyanotriyl groups In addition, as a cyclohexane isocyanate, fluorenyl isocyanophenylphenyl-phenylene isocyanate, the aromatic is large, in terms of suitability and "HD 1) the use of the city g content of 14 200417474 / /; I ο ο %) [Manufactured by Mitsui Takeda Chemical Co., Ltd.] In the reaction between the aforesaid compound containing component (P) and the isoisocyanate compound (Q), the isocyanate group is added to the total hydroxyl groups of the hydroxyl group containing component (P). It is implemented under the condition of excess. There is no specific limitation on the degree of excess. NC 0/0 II is more preferably 1 to 20, more preferably 5 to 15. If the above-mentioned NC〇 / 〇Η ratio exceeds 20, Bay 1J Poor oral performance is poor, and if it is lower than 1, poor adhesion to the steel sheet is caused. The reaction between P) and the polyisocyanate compound (Q) can be carried out using a known catalyst. Examples of the catalyst include tin-based compounds such as dibutyltin laurate or dioctyltin dilaurate, or amine compounds such as TED A or tertiary amine 2,4,6-tris (diamidoaminofluorenyl) benzylphenol or diamidoaminofluorenylphenol, these catalysts can be used alone or in combination. The above-mentioned hydroxyl-containing compound component (P) and the above-mentioned polyisocyanate The reaction of the compound (Q) can be carried out in any organic solvent, such as acetophenone. Then, the unreacted isocyanate containing the isocyanate group-containing polyester polyurethane (A ·) prepared by the above reaction is used with a blocking agent. The group is blocked. As the blocking agent, known compounds such as alcohols, lactams, fatty or / 3-dione blocking agents can be used. In general, regarding their dissociation temperature, alcohols are Above about 180 ° C, lactams are about 160 ° C, oximes are about 140DC, and / 3-diketones are about 100 ° C. Monthly deficiencies are preferably used as a blocking agent. Alcohols And lactam blocking agents It is considered that the stability over time is good, but considering that the better lamination temperature when using the adhesive of the present invention is about 200 ° C, since the difference between the complete dissociation temperature at this lamination temperature is small, the decomposition temperature is 15 3 12 / Explanation of fil 丨 pieces) / 93-03 / 92 丨 37437 200417474 /. /, From the standpoint of the monthly deficient blocking agent is preferred. In addition, the? -Diketones have too low dissociation temperature, Sometimes the stability over time is not good. From this point, it is preferable to use oximes, and it is particularly suitable to use acetophenone. The content of the block-type isocyanate-containing polyester polyurethane (A) in the adhesive of the present invention is preferably 60 to 90% by weight, more preferably 70, with respect to the weight of the entire solid content of the adhesive. ~ 80% by weight. If the content of the block-type isocyanate-containing polyester polyurethane (Λ) exceeds 90% by weight, adhesion to the plastic film may be poor, and if it is less than 60% by weight, it may sometimes be difficult to adhere to the plastic film. Poor adhesion of the steel plate. The adhesive of the present invention contains an epoxy resin (B). By containing this epoxy resin (B), it is possible to impart adhesion to a steel sheet, moisture resistance, and boiling water resistance. The epoxy resin (B) is not particularly limited, and an epoxy phosphate ester (b 1) is preferably used. By containing the epoxy phosphate resin (b), the adhesion to the steel sheet and the moisture resistance can be improved. The epoxy phosphate resin (b 1) is a compound obtained by reacting an epoxy group and a phosphoric acid, the epoxy group is ring-opened, and an epoxy resin portion and a phosphoric acid portion are bonded by a phosphate ester bond. The preferred epoxy phosphate resin (b 1) is a compound represented by the general formula (1), or a compound represented by the general formula (2). 〇 (1) 16 H〇 --P · --〇--d1

I

OH (where R 1 is an epoxy resin residue) 3 12 / ¾ Explanation 丨 丨 丨: (_ Π:) Λ) 3-03 / 92 丨 37437 200417474 〇

2 II R Ο-Ρ-Ο- ^ (2) 〇Η (where R j and R 3 are epoxy resin residues) A particularly preferred epoxy phosphate resin (b 1) has a phosphate group and As the primary hydroxyl compound, a particularly preferred epoxy phosphate resin (b 1) is a compound represented by the general formula (3). OH OH 〇

I I II CH2- CH-R4-〇-P-OH (3)

OH (where IT1 is an epoxy resin residue). As the epoxy phosphate resin (b 1), a commercially available product can be used, and specifically, D E R 6 2 1-E B 50 [D0W. Chemical (stock), solid content 50%] can be used. In addition, a compound having the same characteristic value as that of the above-mentioned D E R 6 2 1-E B 50 can be used as appropriate. When an epoxy phosphate resin (b 1) is used as the epoxy resin (B), 100 parts by weight with respect to the solid content of the block polyisocyanate-containing polyester polyurethane (Λ), The adhesive of the present invention may preferably contain the above-mentioned epoxy phosphate resin (b 1) 0.5 to 3.5 parts by weight, more preferably 1.5 to 2.5 parts by weight. If the content of the epoxy phosphate ester resin (b 1) exceeds 3.5 parts by weight, the compatibility with the component (A) may be deteriorated, and the penetration property with steel plates and plastic films may be poor. 0.5 parts by weight, it may adhere to steel plates 17 312 / Explanation of invention〗 1 丨: (_piece) / 93-03 / 92 丨 37437 200417474 / Poor adhesion and moisture resistance. The epoxy resin (B) may contain a non-phosphoric acid modified epoxy (b 2) instead of the epoxy phosphate resin (b 1), or may further contain a non-phosphoric acid modified resin in addition to the epoxy ester resin (b 1). The preferred epoxy resin (b 2) contains both (b 1) and (b 2). The non-phosphoric epoxy resin (b 2) refers to a resin different from the epoxy phosphate resin (b 1) described above, and refers to any epoxy resin that has not been modified with phosphoric acid. Therefore, the acid-modified epoxy resin (b 2) may be a hydroxyl-free epoxy resin (b 2 -hydroxyl-containing epoxy resin (b 2-2)). A hydroxyl-free epoxy resin (b 2-1) is appropriately used. In addition, if a hydroxyl-free epoxy resin (b 2-1) is used as the phosphoric acid-modified epoxy resin (b 2), The adhesive of the present invention imparts properties and adhesion to steel plates. As such a hydroxyl-free epoxy (b 2-1), for example, a phenol novolac epoxy resin and / or a novolac epoxy resin can be used. It is preferred to use a novolac novolac type cyclic grease. There is no specific limit to the number average molecular weight of a phenol novolac type epoxy resin or a novolac type novolac type, and it is preferably 3 0 0 to 8 0 0, 4 0 0 ~ 6 0 0. As a 曱 δ fraction-varying varnish-type epoxy resin, a commercial product can be used, preferably ARALDITEC Ν 1 2 7 3 [made by Asahi Kasei Epoxy Co., Ltd. with respect to the above-mentioned block polyester containing isocyanate groups The solid content of polyurethane S is 100 parts by weight. The adhesive of the present invention may contain the above The hydroxy-based epoxy resin (b 2-1) is preferably 2 to 6 parts by weight, and more preferably parts by weight. If the content of the above-mentioned epoxy-free epoxy resin (b 2-1) is 6 parts by weight, Poor processability. If it is less than 2 parts by weight, 3 12 / Invention Specification (Supplement) / 93-03 / 92137437 Resin phosphoric acid, post-modified epoxy non-phosphorus 1) or the non-heat-resistant resin 曱 phenol oxygen tree Oxygen tree is better commercially available] 〇1 (A) If it is not contained 4 to 5, the heat 18 200417474 / properties and the adhesion to the steel plate become poor. In addition, when it contains 4 to 5 parts by weight, excellent heat resistance and adhesiveness can be obtained. In addition, if a solid epoxy resin [such as EP 1 K 0 TE 1 0 0 1] is used as the above-mentioned hydroxyl-containing epoxy resin (b 2-2), since it is only blocked with a polyester polyurethane having an isocyanate group, The ester (A) is mixed, and the hydroxyl group of the hydroxyl-containing epoxy resin (b 2-2) does not react with the isocyanate group of the polyester polyurethane (A) containing the isocyanate group. However, when the adhesive is heated after coating, the blocked isocyanate groups are deblocked and free isocyanate groups reappear. The free isocyanate groups can be combined with the hydroxyl groups contained in the solid epoxy resin to function as an adhesive Functions. The adhesive of the present invention may preferably contain the above-mentioned hydroxyl group-containing epoxy resin (b 2-2) with respect to 100 parts by weight of the solid content of the above-mentioned isocyanate group-containing polyester polyurethane (Λ). 1 to 7 parts by weight, more preferably 3 to 5 parts by weight. If the content of the above-mentioned warp-group-containing epoxy resin (b 2-2) exceeds 7 parts by weight, the processability is poor, and if it is less than 1 part by weight, the adhesion to the steel sheet may be poor. The adhesive of the present invention further contains an acid-modified polyene resin (C). By using an acid-modified polyene resin (C), the adhesiveness with polyene can be improved especially. The acid-modified polyene resin can be produced, for example, by graft polymerization of a polyene resin and an acid anhydride containing an ethylenically unsaturated group. Examples of the polyolefin resin include polyethylene glycol, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer. Examples of the acid anhydride containing an ethylenically unsaturated group include maleic anhydride, fumaric anhydride, maleic acid, fumaric acid, and methylene succinic acid. Dried with kawaic acid S. 19 200417474 Also, as the acid-modified polyene resin, a monomer of a copolymer of an olefin and a carboxylic acid containing an ethylenically unsaturated group (such as an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer) may be used. Or a mix. In the adhesive of the present invention, the content of the acid-modified polyene resin (c) is the solid content ratio (A / C) of the isocyanate group-containing polyester polyurethane (A), It is preferably 5 0/5 0 to 9 0/1 0, and more preferably 7 5/2 5 to 8 0/2 0. If the content of the acid-modified polyene resin (C) is higher than the solid content ratio (A / C) 50/50, the adhesion to the steel sheet may be poor, and the coatability may be poor due to the increase in viscosity. If it is less than 90/10, the adhesiveness with a plastic film may become poor. If the content of the acid-modified polyene resin (C) is in the range of the solid content ratio (A / C) 7 5/2 5 to 8 0/2 0, an appropriate adhesive viscosity can be obtained, and excellent Coating performance. The adhesive of the present invention can be prepared by simply mixing the above-mentioned block polyester isocyanate-containing polyester polyurethane (A), the above-mentioned epoxy resin (B), and the above-mentioned acid-modified polyolefin resin (C). The above mixing may be performed in an organic solvent such as an aliphatic ketone (such as ethyl ethyl ketone) or an alicyclic ketone (such as cyclohexanone), and an aliphatic ester (such as ethyl acetate or butyl acetate) may be used simultaneously. The order of the above mixing is also not limited. For example, the above-mentioned isocyanate group-containing polyester polyurethane (A) and the above-mentioned epoxy resin (B) may be mixed first, and then the above-mentioned acid-modified polyolefin resin (C) may be added, or the above-mentioned The epoxy resin (B) and the acid-modified polyene resin (C) are mixed, and then the above-mentioned block polyester isocyanate-containing polyester polyurethane (A) is added, and the above-mentioned block-containing isocyanate group-containing polyester resin (A) may be added first. The X polyester polyurethane (A) is mixed with the above-mentioned acid-modified polyolefin resin (C), and then the above-mentioned epoxy resin (B) is added. 20 312 / Invention Specification (Supplement) / 93-03 / 92137437 200417474 There is no specific limitation on the ability of the plastic film to be laminated on the steel plate plastic film using the adhesive of the present invention. If the adhesive of the present invention is used, it is sufficient to gather difficult-to-bond materials. An olefin film is laminated on a steel plate. Examples of the polyolefin include polyethylene or polypropylene. There is no specific limitation on the lamination of the polyolefin film, and a thickness of about 50 0 // ni can be used. # There is no specific limitation on the steel plate, and a general steel plate substrate such as a zinc-based steel substrate can be used. . Regarding galvanizing of the above-mentioned zinc-bonded steel substrate, a steel plate may be used as a base material, and pure zinc plating or plating may be applied thereto, or a plurality of other plating layers may be applied thereto. If necessary, these steel sheet substrates may be subjected to an underlayer treatment. Stainless steel plates do not need to be specially subjected to an underlayer treatment. However, the adhesion to a polyolefin film can be further improved by chrome. For zinc plating, it is sometimes necessary to perform either of phosphate treatment or chromate treatment. By these chromate treatments and / or phosphoric acid treatments, the adhesion of the baked film in the thin film laminated steel sheet can be increased. There are no specific restrictions on glass manganese and chromate treatment, and conventional routines can be used. In the production of the thin film laminated steel sheet of the present invention, the adhesive of the present invention is applied to the steel surface. At this time, the applied adhesive is smoked to a dry state adhesive layer at a temperature of 180 ° C or higher, preferably at a temperature of 200 to 230 ° C. Here, the adhesive surface after baking and drying can be produced by laminating a polyolefin film by heating. The conditions for thermal lamination vary depending on the type of film and adhesive. For example, it can be pressed at a pressure of 1.0 to 5.0, a lamination temperature of 180 to 2 2 0 ° C, and 5 to 2 0. 丨 丨〖/ Minute 3 丨 2 / Invention Oath (Supplement) / 93-03 / 92 丨 37437. The thickness of the agent can be thin film. Zinc alloy on the surface of wood or plating. For the steel plate at the acid salt, one or more coatings that can improve the surface of the salt treatment method into the plate: baking, in shape, according to the linear speed 21 200417474 degrees of 0 k g / cm: Polyene. <Examples> The present invention will be specifically described below by way of examples, but these examples do not limit the scope of the present invention. In the following production examples, examples, comparative examples, and physical property evaluations, “parts” and “if there is no particular limitation are based on weight, and the units of the base value and the acid value are mg K 0 H / g. Production Example 1 &gt; After the reactor was filled with nitrogen, 5 56 parts of ethyl ethyl ketone (M EK) was added, and then polyester polyol (ρ 1) (VYL 0 Ν GK) equivalent to 254 parts of solid matter was added. 6 4 0; linear saturated copolyester resin; Tg = 79 ° C; number average molecular weight (M η) 21.8 0 0; hydroxyl value = 5; acid value &lt;4; manufactured by Toyobo Co., Ltd.) and equivalent 3.2 parts of solids containing hydroxyl-containing polysiloxane (KR-216; hydroxyl value = 17 0; solid at 25 ° C; manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as the hydroxyl-containing compound component (P), heated to At a temperature of 50 to 60 ° C, dissolve under stirring, and then add dibutyltin dilaurate equivalent to 0.1 parts of solids and 2,4,6 -tri (equivalent to 0.02 parts of solids). Diamidinoaminofluorenyl) phenol as a catalyst. After dissolution, a polyisocyanate compound (Q) (TAKE) equivalent to 70.3 parts of solid was added. NATED-17 0 N; molecular weight = 5 0 4; NC 0% = 2 1%; hexamethylene diisocyanate trimer (NC 0 terminal prepolymer); manufactured by Mitsui Takeda Chemical Co., Ltd. at 80 ° Heat under C to react the hydroxyl group of the hydroxy-containing compound component (P) and the NC0 group of the polyisocyanate compound (Q) for 3 hours to obtain a polyester polyurethane. The NC 0/0 ratio in this reaction is approximately It is 10. Then, in order to block the remaining unreacted NC 0 groups in the obtained polyester polyurethane, the temperature is cooled to 60 ° C. and the dropping force π 3 0. 2 22 312 / Invention Specification ( (Supplements) / 93-03 / 92 丨 37437 200417474 parts of acetophenone oxime as a blocking agent. At this time, pay attention to the exotherm, and maintain the temperature of the reaction solution at 60 ~ 62. C. After the dropping of the blocking agent is finished , Stabilize at 30 in i η at 60 ° C. Then add 86 parts of cyclohexanone and cool to 40 QC to obtain a block isocyanate-containing polyester with a solid content of 36% Polyurethane (a 1). (Production Example 2) After the reactor was filled with nitrogen, 4.8 parts of methyl ethyl ketone (M EK) was added, and then the phase was added. Polyol (ρ 1) (VYL 0 Ν GK 6 4 0; manufactured by Toyobo Co., Ltd.) equivalent to 2.0 parts of solids and hydroxyl-containing polysiloxane (p 2) (2.5 parts of solids) KR-2 1 6; manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and hydroxyl-containing epoxy resin (p 3) (AER 2 6 0 0; manufactured by Japan Epoxy Resin Co., Ltd.) equivalent to 13 parts of solids as the hydroxyl-containing compound component ( P), heated to a level of 50 to 60 QC, dissolved under stirring, and then, dibutyltin dilaurate equivalent to 0.1 parts of solids and 2,4 equivalent of 0.02 parts of solids were added. , 6-Tris (difluorenylaminofluorenyl) phenol as a catalyst. After dissolution, a polyisocyanate S compound (Q) (TAKENATEED-1700N; Mitsui Takeda Chemical Co., Ltd.) equivalent to 57.4 parts of solid was added at 80. The mixture was heated at C to react the hydroxyl group of the hydroxyl-containing compound component (P) with the N C 0 group of the polyisocyanate compound (Q) for 3 hours to obtain a polyester polyurethane. The N C 0/0 ratio in this reaction is approximately 10. Then, in order to block the remaining unreacted N C 0 groups in the obtained polyester polyurethane, the temperature was cooled to 60 ° C., and 28.9 parts of acetophenone oxime was added dropwise as a blocking agent. At this time, it is necessary to pay attention to the exotherm. The temperature of the reaction solution is maintained at 60 to 62 ° C. After the addition of the blocking agent is finished, the temperature is set to 30 ni i η at 60 ° C to stabilize it. Then add 109 parts of cyclohexanone, and cool 23 312 / Invention Specification (Supplement) / 93-03 / 92137437 200417474 to 40 ° C. to obtain a blocked polyisocyanate-containing polyester polymer with a solid content of 31%. Carbamate (a 2). (Production Example 3) In the above Production Example 1, except for using the polyester polyol (p 1) [VYL 0 N GK 8 8 0; linear saturated copolyester; Tg = 84QC; number average molecular weight (M η) = 1 8, 0 0 0; hydroxyl value = 5; manufactured by Toyobo Co., Ltd.] instead of polyester polyol (ρ 1) (VYL 0 NG Κ 6 4 0; manufactured by Toyobo Co., Ltd.) used as a hydroxy compound-containing component (P). The operation of Production Example 1 was repeated to obtain a blocked isocyanate group-containing polyester polyurethane (a 3) having a solid content of 36%. In addition, in the reaction for forming polyester polyurethane, the N C 0/0 ratio is approximately 10. (Production Example 4) In the above Production Example 2, the addition amount of the hydroxyl-containing epoxy resin (p 3) (AER 2 6 0; manufactured by Japan Epoxy Resin Co., Ltd.) except for the hydroxyl-containing compound component (P) was changed. The operation of Production Example 2 was repeated so as to correspond to 20 parts of solids, and a block isocyanate group-containing polyester polyurethane (a 4) having a solid content of 31% was obtained. In the reaction for forming polyester polyurethane, the N C 0/0 ratio was approximately 10. (Production Example 5) In the above Production Example 1, the above-mentioned production was repeated except that only the polyester polyol (ρ 1) (VYL 0 NG G κ 6 4 0; manufactured by Toyobo Co., Ltd.) was used as the hydroxyl-containing compound component (P). The procedure of Example 1 gave a blocked isocyanate group-containing polyurethane (a 5) having a solid content of 36%. In the reaction for forming polyester polyurethane, the N C 0/0 ratio ratio is about 10. (Manufacturing example 6) 24 312 / Invention specification (Supplement) / 93-03 / 92137437 200417474 After the reactor was filled with nitrogen, 5 4 6 parts of methyl ethyl ketone (Μ Ε Κ) and equivalent to 200 parts of solid matter were added. The polyester polyol (p 1) (VYL 0 NGK 6 4 0; manufactured by Toyobo Co., Ltd.) was heated and dissolved at 50 ° C. and then cooled to 40. C. 107.6 parts of hexamethylene diisocyanate (H D I) trimer of acetophenone oxime block compound (manufactured by Sumitomo BAYERNURETHANE Co., Ltd .; solid content 7 5%) was added and stirred. This gave a polyester-block isocyanate mixture with a solid content of 36%. The N C 0/0 ratio in the above generation reaction is approximately 10. (Example 1) To 100 parts of the blocked isocyanate group-containing polyester polyurethane (a 1) obtained in Production Example 1, 16.65 parts of cyclohexanone as a solvent was added, in that order Add 1.6 parts of novolac-type epoxy resin (b2) (ARALDIT ECN 1 2 7 3; molecular weight 4 4 0; manufactured by Asahi Kasei Epoxy Co., Ltd.) equivalent to solid parts, 0.83 parts of phosphoric acid epoxy Vinegar resin (b 1) (DER 6 2 1-Ε B 5 0; D 0 W · Chemical Japan Co., Ltd .; solid content 50%) and 7 2. 7 parts of maleic anhydride modified polyene resin dispersion (C) (manufactured by Toyo Ink Manufacturing Co., Ltd .; solid content of 9.5%), then dibutyltin dilaurate equivalent to 0.01 parts by weight of solid was added, and the mixture was sufficiently stirred to dissolve. After cooling to below 40 ° C, the solid content was adjusted to 20% with cyclohexanone to obtain the adhesive of the present invention. (Example 2) In 100 parts of the block isocyanate group-containing polyester polyurethane (a 2) obtained in Production Example 2, 3.5 parts of cyclohexanone and 0. 9 9 parts of phosphate epoxy resin (b 1) (DER 6 2 1-Ε B 5 0; D 0 W · manufactured by Chemical Japan Co., Ltd .; solid content 50%) ί 8 9 5 parts of maleic acid Anhydride-modified polyene resin dispersion (C) (manufactured by Toyo Ink Manufacturing Co .; solid content 25 3 丨 2 / Invention Specification (Supplement) / 93-03 / 92137437 200417474 9.5%), and then added equivalent to 0. 0 1 part of dibutyltin dilaurate, stir thoroughly to dissolve. After cooling to below 40 ° C, the solid content was adjusted by 20% with cyclohexanone to obtain the adhesive of the present invention. (Example 3) In 100 parts of the block isocyanate-containing polyester polyurethane (a 3) obtained in Production Example 3, 16.5 parts of cyclohexanone was used as a solvent, and sequentially Oral equivalent of 1.16 parts of novolac epoxy resin (b 2) (Λ RALD 1 TECN 1 2 7 3; manufactured by Asahi Kasei Epoxy Co., Ltd.), 0.83 parts of phosphate epoxy resin (b 1) (DER 6 2 1-EB 5 0; D 0 W · Chemical Japan Co., Ltd .; solid content 50%) and 7 2. 7 parts maleic anhydride modified polyene resin dispersion (C) (Toyo Manufactured by Ink Manufacturing Co., Ltd .; solid content 9.5%), and then dibutyltin dilaurate, which is equivalent to 0.01 parts by weight of solid matter, was poured in, and stirred to dissolve it. After cooling to below 40 ° C, the solid content was adjusted to 20% with cyclohexanone to obtain the adhesive of the present invention. (Example 4) In 100 parts of the block isocyanate group-containing polyester polyurethane (a 1) obtained in Production Example 1, 5 parts of cyclohexanone was forcefully injected, and the equivalent was sequentially injected.] .1 6 parts solid novolac epoxy resin C b 2) UR Λ LD IT ECN 1 2 7 3; manufactured by Asahi Kasei Ringo Resin Co., Ltd., 0.83 parts phosphoric acid epoxy resin (b 1) (丨 6 2 1-EB 50; Dow · Chemical Japan Co., Ltd .; solid content 50 V) and 64 parts of acid-modified polyene resin dispersion (C) (manufactured by Toyo Ink Manufacturing Co .; solid content 9 5%), and then force σ into dibutyltin dilaurate equivalent to 0.01 parts of solids, and stir to dissolve it. Cool to below 40 ° C and adjust the solid content to 20¾ with cyclohexanone to obtain the adhesive 26 3 12 / hairpin of the present invention (_piece) / 93-() 3/92 丨 37437 200417474 (Example 5) In 100 parts of the blocked isodeuterate group-containing polyester polyurethane (a 4) obtained in Production Example 4, force 3 5 parts of cyclohexyl S as the solvent, and force in order. 9.9 parts of phosphate epoxy resin (b 1 MDER 6 2 1-Ε Β 50; D 0 W · Chemical Japan Co., Ltd .; solid content 50%) and 8 9.5 parts of maleic anhydride Modified polyolefin resin dispersion (C) (manufactured by Toyo Ink Manufacturing Co., Ltd .; solid content: 9.5%), and then 0.1 parts of dibutyltin dilaurate equivalent to 0.1 part of solid was added, and the mixture was sufficiently stirred to dissolve. After cooling to below 40 ° C, the solid content was adjusted to 20% with cyclohexanone to obtain the adhesive of the present invention. (Comparative Example 1) In 100 parts of the blocked isocyanate group-containing polyester polyurethane S (A 5) obtained in Production Example 5, 16.5 parts of cyclohexanone was used as a solvent, in that order. Novolak type epoxy resin (b 2) (ARALD 1 TEC Ν 1 2 7 3; manufactured by Asahi Kasei Epoxy Co., Ltd.) equivalent to 1.16 parts of solid matter, 0.83 parts of phosphate epoxy ester resin Purpose (b 1) (DER 6 2 1-EB 50 0; Dow · manufactured by Chemical Co., Ltd .; solid content 50%) and 7 2 .7 parts of maleic anhydride-modified polyene resin dispersion ( C) (manufactured by Toyo Ink Manufacturing Co., Ltd .; solid content of 9.5%), and then dibutyltin dilaurate equivalent to 0.01 parts of solid was added, and stirred to dissolve it. Cool to below 40 ° C and adjust the solid content to 20% with cyclohexanone to obtain a comparative adhesive. (Comparative Example 2) In 100 parts of the polyester / block isocyanate mixture obtained in Production Example 6, there were 8 parts of cyclohexanone, and 1.6 parts of solid phenolic aldehyde 3 was added in this order. 12 / Invention gown (Supplement) / 93-03 / 92 丨 37437 27 200417474 Varnish type epoxy tree month purpose (b 2) (AR Λ LD 1 TRCN 1 2 7 3; manufactured by Asahi Kasei Epoxy Co., Ltd.), 1.05 Parts of phosphoric epoxy epoxy resin (b 1) (I) l ·: R 6 2 1-[B 5 0; D 0 W. Chemical Co., Ltd .; solid content 50%) and 7 2. 7 parts acid Modified Polyolefin Resin Dispersion (C) (manufactured by Toyo Ink Manufacturing Co., Ltd .; solid content of 9.5%), and then 0.3 parts by weight of dibutyltin dilaurate and 0.0 parts by weight were added. The solid 2,4,6-tris (diamidoaminofluorenyl) benzol is thoroughly stirred to dissolve it. After cooling to below 40 ° C, the solid content was adjusted to 20% with cyclohexanone to obtain a comparative adhesive. (Comparative Example 3) In 100 parts of the block isocyanate group-containing polyester polyurethane (a 5) obtained in Production Example 5, a force α of 16.5 parts of cyclohexyl copper was used as a solvent, in that order. 0.3 parts of hydroxyl-containing polysiloxane (p 2) (KR-2 16; solid at 25 ° C; manufactured by Shin-Etsu Chemical Industry Co., Ltd.), equivalent to 1.1 parts of solid Novolac epoxy resin month purpose (b 2) (ARALDITEC Ν] 2 7 3; manufactured by Asahi Kasei Epoxy Tree month purpose), 0 · 8 3 parts of phosphate epoxy resin (b 1) (1) ER 6 2 1-EB 50; D 0 \ Bu Chemical Co., Ltd .; solid content 50%) and 72.7 parts maleic anhydride modified polyene resin dispersion (C) (manufactured by Toyo Ink Manufacturing Co., Ltd .; The solid contained t 9.5%), and then dibutyltin dilaurate equivalent to 0.01 parts of solid was added, and the mixture was stirred to dissolve it. After cooling to 40 ° C or less, the solid content was adjusted to 20% with cyclohexanone to obtain a comparative adhesive. (Comparative Example 4) Polyene laminated with cyclohexanone @board adhesive [epoxy polyurethane resin and chuanbutene dianhydride modified polyene resin dispersion (C) -based adhesive; East 28 3 12 / hair 丨! Jj explanation; if (fil)) / 93-03 / 92137437 200417474 manufactured by Western Ink Manufacturing Co., Ltd.] was adjusted to 20% to obtain a comparative adhesive. (Comparative Example 5)-Adhesive for polyene laminated steel sheet using cyclohexanone [epoxy polyamine resin, maleic acid Sf modified polyene resin dispersion (C), and rhenium chromate System adhesive; manufactured by Liyang Ink Manufacturing Co., Ltd.] The solid content was adjusted to 20% to obtain a comparative adhesive. Physical property 1 Parity (1) Production of test plate A test plate for evaluating various physical properties of the adhesive of the present invention and the comparative adhesive was manufactured by the following method. That is, an adhesive was applied to a galvanized steel sheet (thickness: 0.5 μm) with a bar coater so that the dry coating film was 4 μin. At this time, a strip-shaped portion without an adhesive coating is left at a portion of the end 10 in ni of the galvanized steel sheet side (see the strip-shaped portion 1 2 a of the uncoated adhesive described below in FIG. 1). The strip-shaped part of the above uncoated adhesive is moved to the rear of the traveling direction, and then sent to an oven (infrared oven equipped with a conveyor belt at 200 ° C), heated for 100 sec, and heated at its strength. Ganggang, j is completed. At this time, a polypropylene film was laminated on the laminator under a pressure of 5 kg / c2 to a thickness of C = 150 μin), and then immediately put into a water tank for rapid cooling to obtain a laminated steel plate. During the lamination operation, the polypropylene film is also extended on the strip-shaped portion of the uncoated adhesive, and the polypropylene film is also extended on the portion where the steel plate does not exist (see FIG. 1 described below). ] 1 b). In addition, in order to stabilize the laminated steel plate, it was left to stand for a night, and the evaluation test was performed using the obtained test plate. 3 29 3 12 / ¾Explanation 丨 1] Humble: (Buzhong) / 93-03 / 92丨 37437 200417474 (2) Normal peel strength First, the small piece 10 shown in Fig. 1 (schematic side view) is cut out from the test plate obtained in the preceding item (1). The small piece 10 is composed of a polypropylene film 11 with a width of 30 mm and a length of 160 nm and a steel sheet 12 with a width of 30 mm and a length of 60 mm. The end 1 2 a of the steel sheet 12 is The strip-shaped part without the adhesive, the laminated part 1 1 a at one end of the polypropylene film is a part with a width of 30 mm and a length of 50 mm, and the rest of the polypropylene film 1 1 1 with the steel plate 1 2 No sticking. In addition, in order to show the laminated state, FIG. 1 is exaggerated in thickness. Next, from this small piece 10, a test piece 20 shown in FIG. 2 (top view) is produced. That is, with a width of 5 mm from both side ends of the polypropylene film 11 of the small piece 10 shown in FIG. 1, two cutting lines are cut in the lengthwise direction with a cutter, and in the non-laminated part, both sides are removed. end. As a result, as shown in FIG. 2, the non-laminated portion 2 1 a of the polypropylene film 21 has a strip shape with a width of 20 mm. In addition, in the polypropylene film 21, the polypropylene film was cut in the laminated portion 2 1 b adhered to the steel plate to the surface of the steel plate with the blade edge of a cutter to form two cutting lines 23a, 23b. The interval between the cutting lines 23a and 23b is 20 mm. The steel plate 22 includes a strip-shaped portion 2 2 a where the adhesive is not applied and a portion 22 b where the adhesive is applied. A test piece 20 shown in FIG. 2 is mounted on a tensile tester. That is, the end X of the strip-shaped portion 2 2 a of the steel plate 2 2 not coated with the adhesive is clamped to the lower chuck, and the end Y of the non-laminated portion 2 1 a of the polypropylene baking film 21 is clamped to the upper chuck. , The end Y of the non-laminated portion 2 1 a was rotated in a direction of 180 °, the upper chuck was moved at a speed of 50 nuu / ni i η, and the film was peeled from the test plate to measure the strength at this time. 30 312 / Invention Specification (Supplement) / 93-03 / 92137437 200417474 (3) Peel strength after immersion in boiling water Manufacture the same test piece as test piece 20 shown in Fig. 2 and take it out after immersion for 2 hours. After being left for half a day, the measurement was performed by the same method as the "peel strength" (2) above. (4) Peel strength after the moisture resistance test The same test piece as the test piece 20 shown in Fig. 2 was manufactured, and the humidity was 9 8 After being placed in a constant temperature and humidity machine for two weeks, it is taken out, and after being left, it is determined by the same method as the "normal peel strength" in the previous (2). (5) The normal scratch-cup protrusion test is from the previous (1) The manufactured test plate was manufactured into a laminated test piece of 60 mm X 60 mm, as shown in FIG. 3 (schematic oblique view), and a polypropylene film 3 was cut and pressed on the steel plate 3 2 of the laminated test piece. 1Upper cutting line 3 3 a, 3 3 b, 3 3 c, and 3 3 d to make a scratch test piece On the scratch test piece 3 0, make a pair of two parallel cutting lines 3 3 a, the other The two parallel cutting lines 3 3 c and 3 3 d are perpendicular to each other with a distance of 5 ni m, and a central head 3 4 of 5 mm X 5 mm is formed in the central part. The lines 3 3 a, 3 3 b, 3 3 c, and 3 3 d bring the tip of the cutting edge of the polypropylene film 31 to the surface of the steel sheet. In addition, FIG. 3 is for the schematic state of lamination and the formation of the cutting line Therefore, the steel sheet and thickness, and the distance between cutting lines are exaggerated. Then, this scratch test piece 30 is mounted on the center x of the steel plate 3 2 of the test piece 30 on the cup tester. Contact the top of the hemispherical cup for extruding the cup from the surface of the part, and the steel plate 32 faces the polypropylene 312 / Invention Specification (Supplement) / 93-03 / 92137437 in boiling water, "normally 40 ° C and half a day for size measurement The knife in the layer ^ cut out 4 30. Except 3 3b and the spacers, respectively, make the film to show the film 'in the film of the test machine 31 200417474 3 1 squeeze out the extruded hemisphere 7 in in, and scratch the test piece 3 0 The central head 3 4 has a hemispherical bulge in the center. The peeling state of the polypropylene baking film of the raised central head 34 was visually judged. (β) Scratching a cup with a cup of heat and an inch heat test Place the test piece after the cup with a cup produced in (5) above in a hot air oven at 150 ^ C for 1 hour, and then visually judge the peeling state of the film . (7) Scratch-cupping test after immersion in boiling water After immersing the laminated test piece manufactured in (5) above in boiling water for 2 hours, let it stand for half a day, and pass the "cupping test with (5) above" ”In the same operation, use a cutter to form 4 cutting lines 3 3 a, 3 3 b, 3 3 c, and 3 3 d, extrude 7 mm on a cup protrusion tester, and visually judge the peeling of the polypropylene film on the center head. status. (8) Salt water spray test after scratches and cup protrusions After the scratch test piece 30 shown in FIG. 3 was extruded by 6 mm with a cup protrusion tester, a saline spray of 3 ° C and a salt concentration of 5% was put into the spray. The tester was taken out after 48 hours, and the peeling state of the polypropylene film in the center of the test piece was visually judged. (9) The tensile notch test is shown in FIG. 4 (top view), and the test plate obtained in (1) above is cut to a width of 30 using the lamination direction (direction of arrow A in FIG. 4) as the width direction. The length of in in? is 1 2 0 nm, and a tensile notched test piece 40 is manufactured. A center line c is drawn on the laminated film 41 of the tensile notch test piece 40, and parallel lines a and b are respectively drawn at positions 2 5 ηηη from both sides of the center line c. In addition, on the surface of the bell-zinc steel sheet carrying the laminated film 41, the center is also drawn on the part corresponding to the center 32 3 12 / Invention Specification (Supplement) / 93-03 / 92137437 200417474 line C line. Then, this tensile notched test piece 40 was stretched from both ends (directions of arrow B and arrow C in FIG. 4) on an A in s 1 er tester, and stretched by 20% to make the middle band-shaped portion The width (between the parallel lines a and b) (50 mm) becomes 6 0 1 丨] wide. Then cut the polypropylene film along the above-mentioned center line c with the tip of a cutter to reach the surface of the steel plate to form a cutting line. Then, as shown in FIG. 5 (schematic side view), it is mounted on a bending tester so that the side of the laminated film 41 on the side of the laminated film 41 of the tensile notched test piece 40 'after the stretching treatment is the surface side, and is plated. The zinc steel plate 42 is the back side, and the pillar rod 5 5 (diameter = 2 mm) is placed in the middle part of the key steel plate 42, and the cut is bent in the direction of the arrow D in FIG. 5 to make the cutting line of the center line c above. It is the apex of bending, and the surfaces bent to the galvanized steel plate 42 are completely in close contact with each other. The peeling state of the tensile notch test piece 40 'on the laminated film 4 1 along the above-mentioned cutting line on the laminated film 4 1 was visually judged. (10) Heat-resistant tensile notch test The tensile notch test piece (9) above was placed in a hot air oven at 150 ° C for 1 hour, and then the peeling state of the film on this test piece was visually judged. (1 1) Judgment criteria Peel strength is expressed in units (N / 20 mm). The cup protrusion test and tensile notch test are evaluated in the following five levels. ◎: Excellent ◎ _: Slightly excellent 〇: Good, △: Possible 33 312 / Explanation window (Supplement) / 93-03 / 92137437 200417474 x • Inferior The results are shown in Table 1. 34 3 丨 2 / Invention Specification (Supplement) / 93-03 / 92137437 200417474 Table 1 Normal peel strength (N / 20cni) Peel strength after boiling water immersion (N / 20cm) Peel strength after moisture resistance test (N / 20cm) Normal scratches-Cup bump test Scratches-Heat resistance test after cup bumps Scratches after boiling water immersion-Cup bump test scratches-Cup bump brine spray test Tensile notch test Heat resistant notch test Example 1 Film break 52 51 ◎ ◎ _ ◎ _ ◎ ◎ _ _ Example 2 Film break 53 53 ◎ _ _ ◎ ◎ _ _ _ Example 3. 56 47 49 ◎ _ _ _ _ _ Example 4 30. 20 25 ◎ Δ Δ ○ 〇〇Δ Implementation Example 5 Film break 48 45 ◎ Δ ◎ ◎ _ _ Comparative Example 1 Film break 53 53 ◎ X ◎ ◎-◎ _ _ Comparative Example 2 Film break 43 38 ◎ X ◎ ◎ _ Comparative Example 3 10 or less 10 or less 10 or less XXXXXX Comparative Example 4 Film break 48 53 ◎ __ XX ◎ ◎ 'Comparative Example 5 Film break 48 53 ◎ XX ◎ 35 3 丨 2 / Invention Specification (Supplement) / 93-03 / 92137437 200417474 If the adhesive of the present invention is used , Even on steel plates Like the case of pressing hard polyene film adhesive resin film, exhibits excellent heat resistance after the lamination process, at the same time, the boiling water resistance test also ensures excellent adhesion. In particular, compared with the case where an acid-modified polyolefin resin is used alone, the heat resistance after processing is significantly improved, and at the same time, the adhesion after the boiling water resistance test is extremely well secured. In addition, the adhesive of the present invention is not a two-liquid phase type, but a one-liquid phase type. Therefore, it is advantageous in terms of operability, and although it is a one-liquid phase type, its stability over time is also good. Furthermore, if the adhesive of the present invention is used, particularly in the case of laminating a non-adhesive resin film such as a polyolefin film on a steel sheet, a pretreatment such as a corona discharge treatment or a plasma treatment is not required. [Brief Description of the Drawings] Fig. 1 is a schematic side view of a small piece for producing a test piece for a peel test in an example of the present specification. FIG. 2 is a plan view of a test piece for a peel test in an example of the present specification. Fig. 3 is a schematic perspective view of a scratch test piece used for evaluation of physical properties in an example of the present specification. Fig. 4 is a plan view of a tensile notch test piece used for physical property evaluation in the examples of the present specification. Fig. 5 is a schematic side view showing a state in which the tensile notch test piece of Fig. 5 is mounted on a bending tester in a bent state.

(Explanation of component symbols) Y 10 test plate small piece 36 3 12 / Invention specification (Supplement) / 93-03 / 92137437 200417474 1 1, 2 1, 3 1, 4 1 Polypropylene film 1 1 b, 2 1 a Non-layer Pressing section 1 2, 2 2, 3 2, 4 2 Steel plate 11a, 21b Laminated section 1 2 a, 2 2 a Strip-shaped section without adhesive 2 2 Test piece 22b Adhesive-coated sections 23a, 23b, 33a, 33b, 33c, 33d Cutting line 3 0 Scratch test piece; 34 Central head 4 0 Stretch notch test piece 5 5 Pillar rod 37 3 丨 2 / Invention specification (Supplement) / 93-03 / 92 丨 37437

Claims (1)

200417474 Scope of patent application: 1. An adhesive, characterized in that it contains: (1) a polyester polyurethane (A) containing a block of isocyanate groups. The total of the hydroxyl group and the isocyanate amount of the hydroxyl group-containing compound component (P) of the polyol (p 1) and the silicon-containing compound (ρ 2) is obtained by combining the above-mentioned hydroxyl-containing compound component (P) with the polyisocyanate. (Q) the unreacted isocyanate group in the isocyanate group-containing polyester polyamine (A ') obtained by the reaction is obtained by agglomerating; (2) an epoxy resin (B); and (3) an acid-modified polyene resin ( C). 2. The adhesive according to item 1 of the patent application range, wherein the cyclic lipid (B) contains an epoxy phosphate ester lipid (b 1). 3. The adhesive according to item 2 of the patent application scope, wherein the cyclic lipid (B) further contains a non-phosphoric acid modified epoxy resin (b 2). 4. The adhesive according to item 3 of the patent application scope, wherein the non-modified epoxy resin (b 2) is an epoxy resin that does not contain a hydroxyl group. 5. In the adhesive according to any one of claims 1 to 4, the above-mentioned hydroxyl-containing compound component (P) further contains a hydroxyl-containing cyclolipid (ρ 3). 6-A method for producing an adhesive, It is characterized in that the polyhydric alcohol (ρ 1) and the hydroxyl group-containing polylithium oxo compound (ρ 2) contain a total of hydroxyl groups of the warp compound component (P), and the isocyanate group is excessive, and the content of the isocyanate group is excessive. Hydroxyl compound component (P) \ reacts with polyisocyanate compound (Q) to prepare polyester polyurethane (A ') containing isocyanate group, and then use block 312 / Invention Specification (Supplement) / 93-03 / 92丨 37437 is composed of a compound-based peresterified acid ester oxytree oxytree phosphoric acid, the oxygen tree of which includes an amidating agent, and the preparation will be 38 200417474 in the above-mentioned polyester polyamine sulfonate (A ') containing an isocyanate group. The unreacted isocyanate group is formed into a block to prepare a polyester polyurethane (A) containing a blocked isocyanate group, and then the polyester polyurethane (A) containing the block isocyanate group and an epoxy resin (B ) And acid-modified polyene resin (C). 7. The manufacturing method according to item 6 of the scope of patent application, wherein the above-mentioned polyester isocyanate group-containing polyester polyurethane (A), epoxy phosphate resin (b 1), and non-filled acid-modified ring Oxygen purpose (b 2) is mixed with the acid-modified polyolefine purpose (C). 8. The manufacturing method according to item 6 of the scope of patent application, wherein a polyester polyamine containing a blocked isocyanate group is prepared by using a warp-containing compound (P) further containing a warp-containing epoxy resin (ρ 3). Phosphonate (a 1), and then a polyisocyanate (a 1) containing a block isocyanate group, an epoxy phosphate resin (b 1), and an acid-modified polyene resin (C) are mixed . 9. A plastic film laminated steel plate, characterized in that a plastic film and a steel plate are laminated by using an adhesive of any one of claims 1 to 4 of the scope of patent application. 1 0. A plastic film laminated steel plate characterized in that the plastic film and the steel plate are laminated by using an adhesive in the scope of patent application No. 5. 39 312 / Invention Specification (Supplement) / 93-03 / 92137437