WO2004011246A1 - Method for manufacturing aluminum laminate and aluminum laminate - Google Patents

Abstract

A method for manufacturing an aluminum laminate which comprises the steps of:(1) applying a curable resin composition comprising an epoxy acrylate oligomer, an acrylic monomer and a curing agent on an aluminum base material, and (2) carrying out at least one of the following curing treatments, irradiation with a radiation and heating, to thereby cure the above curable resin composition; and an aluminum laminate manufactured by the method. The aluminum laminate can be advantageously used for an aluminum tube, such as the one for a medicine, which requires sufficient flexibility to endure repeated bendings and/or stretchings.

Description

 Description Method of making aluminum laminate and aluminum laminate

 The present invention relates to a method for producing an aluminum laminate and an aluminum laminate, and more specifically, requires excellent concealing properties and flexibility, or excellent adhesion of a cured coating film, such as a pharmaceutical aluminum tube. The present invention relates to a production method suitable for manufacturing an aluminum laminate to be manufactured and an aluminum laminate having such characteristics. Background art

 Aluminum tubes for pharmaceuticals, which contain contents such as drugs and chemicals, need to be repeatedly bent and extended to take out the contents. For this reason, coating films provided on the inner and outer surfaces of aluminum tubes are required to have excellent flexibility and excellent adhesion to aluminum surfaces.

 Therefore, as a coating material for aluminum tubes, a heat-curing coating agent composed of an epoxy-based cured product and a urethane-based cured product containing a large amount of an organic solvent has been mainly used. Therefore, after coating these heat-curable coating agents on the aluminum surface, the coating is heated at, for example, 180 ° C. for about 1 minute to 10 minutes to evaporate the organic solvent and heat the coating. There is a method in which a curable coating agent is cured to form a coat film.

However, such a heat-curable coating agent contains a large amount of an organic solvent, and problems such as the deterioration of the working environment, the burden on flameproofing equipment, and the effects of environmental release caused by the organic solvent have been raised. . In addition, when using such a heat-curable coating agent, a prolonged heat treatment is required. Because of the necessity, there were many problems such as the production line becoming large-scale and consuming a large amount of production energy.

 Therefore, Japanese Patent Application Laid-Open No. Hei 9-140760 discloses an ultraviolet-curable resin composition capable of forming a coating film having excellent adhesion to plastic films and metals, and a coating agent containing the same. ing. More specifically, a UV-curable resin composition comprising the following components (A), (B) and (C) and a coating agent containing the same are disclosed.

 (A) Liquid epoxy resin: 100 parts by weight

 (B) Photodynamic thione polymerization initiator: 0.5 to 30 parts by weight

 (C) At least one kind of resin selected from petroleum resin, perpen resin, and rosin resin: 3 to 100 parts by weight

 However, the disclosed ultraviolet-curable resin composition has a problem that the curing speed of the liquid epoxy resin is low, and therefore, the productivity is low. In addition, when applied to an aluminum substrate and the aluminum substrate is bent, there is a problem that the cured coating film is easily peeled off. Furthermore, since the disclosed ultraviolet-curable resin composition uses a relatively large amount of liquid epoxy resin and other resins, it has a problem that it has a high viscosity and is difficult to handle and form a thin film.

 Therefore, Japanese Patent Application Laid-Open No. H10-1683885 discloses a UV-curable can coating composition capable of forming a coating film for can coating having excellent adhesion and abrasion resistance, and the like. A method for producing a coated metal can using the ultraviolet-curable can coating composition is disclosed. More specifically, a UV-curable can coating composition comprising the following components (A), (B) and (C), and a method for producing a coated metal can using the UV-curable can coating composition Is disclosed.

 (A) A polyester having a hydroxyl group (a), a compound having a cyclic ether and a (meth) acryloyl group in one molecule (b), and an ultraviolet-curable resin obtained by ring-opening addition of the compound: 5 to 95 parts by weight

(B) Radical polymerizable unsaturated group-containing compound: 5 to 95 parts by weight (c) Photopolymerization initiator: 0.1 to 10 parts by weight

 However, the total amount of (A) and (B) is 100 parts by weight.

 In addition, Japanese Patent Application Laid-Open No. 11-2466878 discloses an ultraviolet-curable coating composition capable of forming a coating film having excellent hardness and abrasion resistance. More specifically, an ultraviolet-curable coating composition comprising the following components (A) and (B) is disclosed. In Examples, an ultraviolet-curable coating composition containing 7% by weight of a photopolymerization initiator is disclosed. Is disclosed.

 (A) Ethylene unsaturated compound: 100 parts by weight

 (B) Aluminum oxide: 20 to 45 parts by weight

 However, since the coating composition for ultraviolet-curable cans disclosed in Japanese Patent Application Laid-Open No. 10-168385 uses a polyester (a) having a hydroxyl group, the resulting cured coating film has an ultraviolet ray. While the curability and flexibility tended to be insufficient, there was a problem that it was easily hydrolyzed due to the moisture present in the surroundings.

 In addition, when the ultraviolet-curable can coating composition is applied to an aluminum substrate and the aluminum substrate is bent, there is a problem that the cured coating film is easily peeled off.

 Further, the ultraviolet-curable coating composition disclosed in Japanese Patent Application Laid-Open No. H11-2467888 requires a large amount of aluminum oxide to be added, and the resulting cured coating film has insufficient ultraviolet curing. On the other hand, aluminum oxide was easily precipitated, and it was difficult to obtain a cured coating film consisting of a uniform thin film.

 In addition, there is a problem that the aluminum oxide and the hardened component are easily separated, and when the aluminum base material is applied and the aluminum base material is bent, the hardened coating film is easily peeled off. Was seen.

The present invention solves the conventional problems, and includes a step of laminating a specific curable resin composition on an aluminum substrate. Thus, an aluminum substrate such as a pharmaceutical aluminum tube is provided. Even if it is bent, the cured coating film is less likely to peel off easily. It is an object of the present invention to provide a method for producing an aluminum laminate, which can easily and quickly produce a film laminate, and an aluminum laminate. Disclosure of the invention

 According to the present invention, there is provided a method for producing an aluminum laminate, which includes the following steps (1) and (2), and can solve the above-mentioned problems.

 (1) A step of laminating a curable resin composition containing an epoxy acrylate oligomer having a polar group, an acrylic monomer, and a curing agent on an aluminum base

 (2) A step of curing the curable resin composition by performing radiation irradiation and / or heat treatment or one of the curing treatments.

 In other words, by preparing an aluminum laminate in this way, even when the aluminum base material is bent, an aluminum laminate in which the cured coating film is hardly peeled off easily and quickly is formed. can do.

 Further, when the epoxy acrylate oligomer has a polar group, particularly an acid group, compatibility with other components in the curable resin composition is improved, and adhesion to the aluminum base material can be improved. .

 Further, another embodiment of the present invention provides a curable resin composition containing a polar group-containing epoxy acrylate oligomer, an acrylic monomer, and a curing agent on an aluminum substrate. 0 It is an aluminum laminate characterized by having a cured coating film of 1 to 3 mm.

 In other words, with such a configuration, even when the aluminum base material is bent, a hardened coating film (hardened layer) with which the hardened coating film (hardened layer) is less easily peeled can be formed more easily and quickly. Can be created.

In addition, by using the curable resin composition thus configured, (4) The curable resin composition can be easily handled, and can be easily obtained from thin films to thick cured films. BRIEF DESCRIPTION OF THE FIGURES

 1 (a) to 1 (C) are views provided for explaining a method for producing an aluminum laminate of the present invention.

 FIG. 2 is a diagram provided to explain the influence of the acid value of an epoxy acrylate oligomer having a polar group.

 FIGS. 3 (a) and 3 (b) are diagrams used to explain the effect of the type of acrylate monomer on the physical properties of the cured coating film.

 FIG. 4 is a diagram showing a method of laminating the curable resin composition on a tubular aluminum substrate.

 FIG. 5 (a) is a perspective view of the aluminum laminate of the present invention, and FIG. 5 (b) is a cross-sectional view of the aluminum laminate of the present invention.

 FIG. 6 is a diagram provided to explain the effect of the thickness of the cured coating film. FIG. 7 is a cross-sectional view of an aluminum laminate provided with an inner resin layer. BEST MODE FOR CARRYING OUT THE INVENTION

 [First Embodiment]

 As illustrated in FIG. 1, the first embodiment is a method for producing an aluminum laminate 20 including the following steps (1) and (2).

 (1) A step of laminating a curable resin composition 12 containing a polar group-containing epoxy acrylate oligomer, an acrylic monomer and a curing agent on an aluminum substrate 10 (hereinafter referred to as a laminating step) In some cases.)

(2) A step of curing the curable resin composition 12 by performing radiation irradiation 14 and heat treatment, or one of the curing treatments

(Hereinafter, it may be referred to as a curing step.)

In addition, FIG. 1 (a) shows the stage where the aluminum base material 10 was prepared, FIG. 1 (b) shows a step of laminating the curable resin composition 12 on the aluminum base material 10 using the coating device 18. Further, FIG. 1 (c) shows a stage where the applied curable resin composition 12 is cured by irradiation 14 to form an aluminum laminate 20 having a cured coating film 13.

1. Lamination process

 (1) Curable resin composition

 ①Epoxyacrylate oligomer having polar group

 Examples of the epoxy acrylate oligomer having a polar group include an epoxy acrylate oligomer having at least one polar group selected from the group consisting of a phosphate group, a carboxyl group, a sulfonic acid group, and a hydroxyl group. Can be

 Of these, epoxy acrylate oligomers having an acid group such as a phosphate group, a carbonyl group, a sulfonic acid group and the like are more preferable because a cured film excellent in flexibility and adhesion can be obtained. Epoxy acrylate oligomers having a phosphoric acid group are particularly preferred, since a cured coating film having further excellent properties can be obtained and the compatibility with other components is excellent.

 The epoxy acrylate oligomer having such a polar group can be obtained by, for example, obtaining a reactant of a compound having a polar group and bisphenol A glycidyl ether in advance and then acrylizing the reactant. Obtainable.

 Further, the number average molecular weight (Mn) of the epoxy acrylate oligomer having a polar group is preferably set to a value within a range of 500 to 100,000.

The reason for this is that if the number average molecular weight of such an epoxy acrylate oligomer is less than 500, the resulting cured coating film may be hard, and cracking may occur during bending. Meanwhile, such epoxy If the number average molecular weight of the relay oligomer exceeds 10 000, the viscosity of the obtained resin composition becomes high, and it may not be suitable for printing or coating.

 Therefore, the number average molecular weight of such an epoxy acrylate oligomer is more preferably set to a value within the range of 1,000 to 8,000, and more preferably to a value within the range of 1,500 to 5,000. More preferably, The number average molecular weight of each of the epoxy acrylate oligomer and the urethane acrylate oligomer described below can be measured using gel permeation chromatography (GPC).

 Further, the acid value of the epoxy acrylate oligomer having a polar group is preferably set to a value within the range of 5 to 50 mg KOH / g.

 The reason for this is that if the acid value of such an epoxy acrylate oligomer is less than 5 mg KO HZ g, the adhesion to the aluminum substrate is reduced, and when the aluminum substrate is bent, cracks may occur in the cured coating film. That's why. On the other hand, if the acid value of the epoxy acrylate oligomer exceeds 5 Omg KOHZg, the resulting cured coating film may have reduced chemical resistance.

 Therefore, the acid value of such an epoxy acrylate oligomer is more preferably set to a value within a range of 10 to 45 mg KO HZ g, and further preferably set to a value within a range of 20 to 40 mg KO HZ g. . The acid value of such an epoxy acrylate oligomer can be measured by a titration method using KOH.

Here, the effect of the acid value of the epoxy acrylate oligomer having a polar group will be described in detail with reference to FIG. Figure 2 shows the acid value (mg KO HZ g) of the epoxy acrylate oligomer having a phosphate group as a polar group on the horizontal axis, and the vertical axis shows the adhesion evaluation (relative value) of the cured coating film obtained. ) And chemical resistance evaluation (relative value). In addition, regarding the evaluation of adhesion and the evaluation of chemical resistance, the results obtained in Examples described later are obtained. 5 points for evaluation ◎, 3 points for evaluation 、, 1 point for evaluation △, and 0 point for evaluation X. If the evaluation was divided, the average of six evaluation samples was taken as each evaluation point. . For example, in the evaluation of adhesion, evaluation ◎ was obtained with three samples, and evaluation 〇 was obtained with another three samples, the evaluation score of adhesion was set to four.

 As shown in FIG. 2, it can be understood that, when the acid value of the epoxy acrylate oligomer having a polar group is within a predetermined range, excellent adhesion and chemical resistance can be obtained in the obtained cured coating film. However, if the acid value is less than 5 mg KOHZg, the adhesiveness of the cured coating film tends to decrease, and the chemical resistance tends to decrease accordingly. On the other hand, when the acid value exceeds 50 mg KOHZg, the chemical resistance of the obtained cured coating film tends to decrease.

 Therefore, by setting the acid value of such an epoxy acrylate oligomer to a value within the range of 10 to 50 mg KO HZ g, the adhesion and chemical resistance of the cured coating film are further improved, and a rating of 1 or more is obtained for each. It can be easily obtained. By setting the acid value to a value within the range of 20 to 40 mg KOHZg, a higher evaluation of 3 or more can be easily obtained.

②Acryl monomer

Examples of the acrylic monomer to be combined with the epoxy acrylate oligomer having a polar group include methyl (meth) acrylate, ethyl (meth) acrylate, acryloylmorpholine, and isobornyl acrylate. , Vinylcaprolactone, ethyl carbitol butyrate, dicyclopentyl acrylate, 2-ethylhexyl acrylate, 6-hexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl acrylate, tripropylene Dalicol diacrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glyco Di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate dicyclopentanyldi ( (Meth) acrylate, di-cyclopentenyl di (meth) acrylate modified with hydroprolactone, di (meth) acrylate modified with ethylene oxide, hexyl di (meth) acrylate, isocyanurate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, diventryerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, phenyl Nirenzo Xyside-modified trimethylolpropane acrylate (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diproerythrone-modified dipentaerythritol hexane ( One type of meth) acrylate, urethane acrylate, epoxy acrylate, polyester acrylate, and the like, or a combination of two or more types may be used.

 Further, among these acryl-based monomers, it is more preferable to use a combination of acryloyl morpholine and isovonyl acrylate or one of the acryl-based monomers.

 The reason for this is that by using such an acrylic monomer, the viscosity of the curable resin composition can be easily adjusted, the compatibility is improved, and even if the aluminum substrate is bent, This is because it is possible to more easily and quickly prepare an aluminum laminate in which the coating film is less likely to peel off. Also, by using such an acrylic monomer, the flexibility (elongation, etc.) of the cured coating film can be improved without changing the properties such as the strength of the cured coating film.

Here, the influence of the type of the acrylic monomer will be specifically described with reference to FIGS. 3 (a) and 3 (b). In Fig. 3 (a), the horizontal axis is hard Of the three acrylic monomers (IB0A: isobonyl acrylate, TPGDA: tripropylene glycol diacrylate, 2-PEA: 2 monophenoxyl acrylate) in the curable resin composition (% by weight) ), And the vertical axis shows the value of the tensile strength (kgf Z cm ² ) of the cured coating film. In Fig. 3 (b), the horizontal axis shows the amount (% by weight) of the acrylic monomer in the cured green resin composition, and the vertical axis shows the elongation of the cured coating film. (%).

As can be understood from the results shown in FIGS. 3 (a) and (b), for example, isobonyl acrylate (IB0A) is 50% by weight or less of the total amount, that is, 100 parts by weight of epoxy acrylate oligomer. Te, 0.1 - 1 0 0 Li by the used in a range of parts by weight, monitor and to be able to put that pull 5 0 kgf Roh cm ² or more values strength to the cured coating film, cured The elongation of the coating film can be maintained at a high value of 50% or more. Further, the amount of the acryl-based monomer is preferably set to a value within the range of 0.1 to 300 parts by weight based on 100 parts by weight of the epoxy acrylate oligomer.

 The reason for this is that if the amount of such an acrylic monomer is less than 0.1 part by weight, it becomes difficult to adjust the viscosity of the curable resin composition, and printability and coating suitability may decrease. On the other hand, if the amount of the acrylic monomer exceeds 300 parts by weight, the resulting cured coating film may have a reduced degree of chemical resistance.

 Therefore, it is more preferable that the addition amount of the acryl-based monomer be in the range of 5 to 200 parts by weight, and it is more preferable that the addition amount be in the range of 10 to 100 parts by weight.

In addition, it is more preferable that the ratio of acryloyl morpholine and isobonyiacrylate used in the acrylic monomer (100 weight ⁰ / o) is within a range of 50% by weight or more.

The reason for this is that when the use ratio of such acryloyl morpholine and isobonyle acrylate is less than 50% by weight, the addition effect is exhibited. Not only is it not performed, but also the balance of adhesion, flexibility, chemical resistance, etc. of the obtained cured coating film tends to be lost. That is, is the obtained cured coating film peeled off, cracks are generated at the time of bending, or are the rubbing test characteristics due to chemicals deteriorated? · This is because there are cases.

Therefore, among the Akuriru monomer (1 0 0 wt%), Akuri port Irumoruhorin and good re preferred that the proportion of Isoboniruakuri rate Bok and 5 5 by weight _^0/0 or more values, the 6 0 wt% or more More preferably, it is set to a value.

 When acryloyl morpholine and isobonyl acrylate are used together, when the addition ratio of acryloyl morpholine is W 1 and the addition ratio of isobornyl acrylate is W 2, W 1 W 2 It is more preferable to set the ratio to a value within the range of 1 to 100.

 The reason for this is that if the ratio of W 1 ZW 2 is less than 1, the hardness of the obtained cured coating film increases, and cracks may occur at the time of bending and bending. On the other hand, if the ratio of W 1 ZW 2 exceeds 100, the resulting cured coating film may have reduced chemical resistance and scratch resistance.

 Therefore, the ratio of W 1 ZW 2 is more preferably set to a value in the range of 2 to 50, and even more preferably to a value in the range of 5 to 20.

③Curing agent

As a curing agent (photopolymerization initiator), for example, benzophenones, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, methyl compounds such as methylbenzoinfomate, and monoacylphosphinoxide And phosphorus compounds such as bis-nasyl phosphinoxide, thioxanthones and the like, alone or in combination of two or more. More specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl Toluene, benzoin isopropyl ether, benzoin n-butyl ether, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpronone-one, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-methyl-2-ene Morpholinol (4-thiomethylphenyl) propane-one-one, 2-benzyl-2-dimethylamino-111- (4-morpholinophenyl) butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Benzobenzone, o-benzoyl methyl benzoate, hydroxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4, 6—Tris ( (Lichloromethyl) 1-S-triazine, 2-methyl-4,6-bis (trichloride) 1-S-triazine, 2- (4-methoxyphenyl) 4,6-bis (trichloromethyl) -S-triazine Riadin and the like.

 When a thermal polymerization initiator is used, preferred examples thereof include azobisisobutyronitrile (AIBN), benzoyl peroxyside, dicumyl peroxyside, g-butyl peroxyside, and di-t-butyl. Peroxy-1,3,3,5-trimethylcyclohexane, t-butylmethyl peroxide, g-t-amyl peroxide, t-butylhydroperoxide, 2,5-dimethyl-2,5-di- (t-butyl veroxy) — Hexane and the like.

 Further, the amount of the curing agent added is preferably set to a value within the range of 1 to 20 parts by weight based on 100 parts by weight of the curable resin composition.

 The reason for this is that if the amount of the curing agent added is less than 1 part by weight, the resulting curable resin composition has a low curing rate, resulting in reduced productivity and wrinkles during curing. Because there is. On the other hand, if the amount of the curing agent exceeds 20 parts by weight, the resulting cured coating film may have reduced flexibility and chemical resistance.

Therefore, the amount of the curing agent added is set to 100% by weight of the curable resin composition. It is more preferable that the value be in the range of 2 to 15 parts by weight, and it is more preferable that the value be in the range of 3 to 10 parts by weight.

 It is also preferable to add a photosensitizer for accelerating the photopolymerization reaction. Such photosensitizers include, for example, triethylamine, triethanolamine, methyljetanolamine, methyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, And tertiary amines such as 4,4'-getylaminobenzophenone, alkylphosphines such as triphenylphosphine, and thioethers such as thiodiglycol, and the like, alone or in combination of two or more.

④Urethane acrylate oligomer

 Further, in order to further improve the chemical resistance and the scratch resistance in the obtained cured coating film, it is preferable to further add a urethane acrylate oligomer.

 When a urethane acrylate oligomer is added, its average molecular weight is preferably set to a value within a range of 500 to 500,000. The reason for this is that if the average molecular weight of the urethane acrylate oligomer is less than 500, the curing rate of the curable resin composition will be low, the productivity will be low, and the hardness of the cured coating film will increase. This is because cracks may occur during bending. On the other hand, if the average molecular weight of the urethane acrylate oligomer exceeds 50, 000, the resulting cured coating film may have reduced chemical resistance.

 Therefore, the average molecular weight of the urethane acrylate oligomer is more preferably set to a value within the range of 2,500 to 10,000, and more preferably to a value within the range of 3,500 to 500,000. More preferably,

When the urethane acrylate oligomer is added, the amount of the urethane acrylate oligomer to be added should be within a range of 1 to 50 parts by weight based on 100 parts by weight of the epoxy acrylate oligomer. Good Good.

 The reason for this is that if the amount of the urethane acrylate oligomer is less than 1 part by weight, the surface curability of the cured coating film is reduced, and the chemical resistance and the scratch resistance may be reduced. On the other hand, if the amount of the urethane acrylate oligomer exceeds 50 parts by weight, the adhesion of the obtained cured coating film is reduced, and cracking or peeling may occur at the time of bending and bending. is there.

 Therefore, the amount of the urethane acrylate oligomer to be added is more preferably set to a value in the range of 10 to 30, and even more preferably to a value in the range of 15 to 25.

⑤Coupling agent

 In addition, in order to impart even more excellent adhesion to the aluminum substrate in the cured coating film, it is preferable to add a force coupling agent. Such a force coupling agent is defined as a compound having two or more different reactive groups in one molecule, and one of the reactive groups is an inorganic material obtained by hydrolysis, a dealcoholization reaction or a dehydration reaction. An alkoxysilane group or an alkoxytitanium group capable of chemically bonding to an organic material or the like is preferable as another reactive group. For example, a vinyl group, (meta- It is preferable that they are an acryl group, an epoxy group, an amino group or a mercapto group.

 Therefore, a vinyl group-containing silane coupling agent, a (meth) acrylic group-containing silane coupling agent, an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, and a mercapto group-containing silane A single type or a combination of two or more types, such as a system coupling agent, an epoxy group-containing titanium coupling agent, and an amino group-containing aluminum system coupling agent.

Preferred examples of these coupling agents include: -aminopropyltriethoxysilane, r-glycidoxypropyltriethoxysilane. And r-mercaptopropyl trimethoxysilane, vinyltrimethoxysilane, r-aminopropyltriethoxytitanium, r-glycidoxypropyltriethoxyaluminum, r-mercaptopropyltrimethoxytitanium, vinyltrimethoxyaluminum and the like. In the case where an epoxy acrylate oligomer having a phosphoric acid group is used as the epoxy acrylate oligomer having a polar group, a vinyl group-containing epoxy acrylate oligomer is used because a more excellent stability of the curable resin composition is obtained. It is preferable to use trimethoxysilane, (meth) acryl group-containing trimethoxysilane, and epoxy group-containing trimethoxysilane.

 The amount of the coupling agent to be added is preferably set to a value within the range of 0.1 to 10 parts by weight based on 100 parts by weight of the curable resin composition.

 The reason for this is that if the amount of such a coupling agent is less than 0.1 part by weight, the effect of addition will not be exhibited, and the resulting cured coating film will have reduced adhesion during folding and bending and over time. This is because there are cases where On the other hand, if the amount of the coupling agent exceeds 10 parts by weight, the stability and curability of the curable resin composition may be reduced, or the strength of the obtained cured coating film may be reduced. 'Because there is.

 Therefore, the amount of the coupling agent is preferably set to a value within the range of 1 to 8 parts by weight with respect to 100 parts by weight of the curable resin composition, and 4 to 6 parts by weight. More preferably, the value is within the range.

⑥Colorant

 In addition, it is preferable to add an inorganic coloring pigment, an organic coloring pigment, an inorganic filler, an organic filler, an inorganic matte powder pigment, an organic matte powder, and the like as a coloring agent.

In particular, when providing the curable resin composition with concealing properties, it is preferable to use titanium oxide, carbon black, or the like as the coloring agent. When it is desired to obtain more excellent hiding properties by adding an amount, it is more preferable to use rutile-type titanium oxide. In addition, the amount of the coloring agent to be added is controlled by the curable resin composition; The value is preferably within a range of 0.0 to 40 parts by weight based on 100 parts by weight.

 The reason for this is that if the amount of such a coloring agent is less than 0.1 part by weight, the cured film may not exhibit coloring properties. On the other hand, if the amount of the coloring agent exceeds 40 parts by weight, the curability of the curable resin composition may decrease, and the strength of the obtained cured coating film may decrease. .

 Therefore, it is more preferable that the amount of the colorant is in the range of 1 to 40 parts by weight, and more preferably in the range of 3 to 35 parts by weight, based on 100 parts by weight of the curable resin composition. Is more preferable.

⑦Additives

 In the curable resin composition, defoaming agents, leveling agents, silicone oils, lubricants, surfactants, dispersants, antistatic agents, It is preferable to add a compound such as an antioxidant.

 It is also preferable to add a cationic curing type monomer, for example, an epoxy resin or an oxetane resin, together with the cationic curing agent.

⑧Viscosity

Further, the viscosity (measuring temperature: 25 ° C.) of the curable resin composition is preferably set to a value within the range of 100 to 50,000 mPa 2 sec. If the viscosity is less than 100 mPa'sec., The curable resin composition may be difficult to handle or the stability of the curable resin composition may be reduced. Because there is. Meanwhile, such viscosity If the ratio exceeds 50,000 OmPa secsec., The handleability of the curable resin composition may decrease, or the suitability for printing and coating may decrease.

 Therefore, it is more preferable to set the viscosity of the curable resin composition to a value within the range of 500 to 100, OOO m P a ■ sec. It is more preferable that the value be within the range of.

(2) Aluminum substrate

 ① Thickness

 Further, it is preferable that the thickness of the aluminum base material is set to a value within a range of 10 U rr »to 5 mm depending on the use.

 The reason for this is that if the thickness of the aluminum base material is less than 10 m, wrinkles may be easily formed or the mechanical strength of the obtained aluminum laminate may be insufficient. is there. On the other hand, if the thickness of the aluminum base exceeds 5 mm, handling becomes difficult, and lamination with the curable resin composition may become difficult.

 Therefore, the thickness of the aluminum base material is more preferably set to a value in the range of 5 OjUm to 3 mm, and even more preferably to a value in the range of 80 / im to 1 mm.

② Annealing

Preferably, the aluminum substrate is annealed. The reason for this is that by using an annealed aluminum substrate, the adhesion between the cured coating film and the aluminum substrate can be improved, and even when the aluminum substrate is bent. This is because it is possible to easily and quickly produce an aluminum laminate in which the cured coating film is less likely to peel off. As an example of an annealing condition for the aluminum base material, as an example, reheating by rapid heating of 1 ° CZ seconds or more to a temperature within a range of 380 to 530 ° C. After holding for 20 seconds or less, it is preferable to cool at a temperature lowering rate of, for example, 50 ° CZ or more.

③Surface treatment

 Further, it is preferable that at least one surface treatment of an ozone treatment, a plasma treatment, a corona treatment, an ultraviolet treatment and a gay acid flame treatment is applied to the surface of the aluminum base material.

 With this configuration, the adhesion between the aluminum substrate and the cured coating film can be significantly improved.

 In particular, a gay acid flame treatment is a preferable surface treatment because the adhesion between the aluminum base material and the cured coating film can be drastically improved.

 In addition, when performing the gay acid flame treatment, a flame of a fuel gas containing a silane compound having a boiling point of 100 to 100 ° C is sprayed on the aluminum base material entirely or partially. Is preferred.

(3) Lamination method

 The method of laminating the curable resin composition and the aluminum base material is not particularly limited, and examples thereof include a roll coater, a knife coater, an applicator coater, a gravure coater, a screen printing method, a brush coating method, and the like. It is preferred to use

 Here, referring to FIG. 4, a method of laminating (coating) the curable resin composition 52 on the surface of the tube-shaped aluminum base material 56 using a roll coater 54 will be specifically described. Will be explained.

First, the unpainted tubular aluminum base material 56 is positioned at the position shown by the symbol S with respect to the rotary support plate 55 that rotates continuously in the direction of the arrow shown by the symbol B around the symbol C. Be attached. Not shown However, it is preferable that a fixing rod for fixing the tubular aluminum base material 56 be provided on the surface of the rotary support board 55.

 Next, the unpainted tubular aluminum base material 56 rotates from the position indicated by the symbol S to the position indicated by the symbol P, and presses against the surface of the roll coater 54. At this time, the roll coater 54 rotates in a direction indicated by an arrow A to remove a predetermined amount of the curable resin composition 52 from a pan 53 provided below the roll coater 54. It is preferable that it is configured so that it can be lifted. Then, the curable resin composition 52 is transferred from a roll coater 54 holding a predetermined amount of the curable resin composition 52 on the surface thereof to a tubular aluminum base material 56 and laminated. Will be. Although not shown, a blade for adjusting the amount of the curable resin composition 52 held on the surface of the mouth coater 54 is preferably provided.

 Next, the tubular aluminum laminate 30 on which the curable resin composition 52 has been laminated is rotated to the position indicated by the symbol F, detached from the rotary support board 55, and then moved to the next step. For example, it is transferred to a drying step or an ultraviolet irradiation step.

 By carrying out in this manner, the curable resin composition 52 can be quickly and uniformly laminated to a uniform thickness using the roll coater 54 even for a tubular aluminum base material. .

2. Curing process

 (1) Irradiation

The curable resin composition upon to radiation curing, for example, using a Metaruhara I Doranpu or ultraviolet lamp, it is preferable that the lamp integrated quantity of light to a value within the range of 1 0 0~ 1, 5 0 0 m J cm 2 .

The reason for this is that if the integrated light amount of the lamp is less than 100 mJcm ² , the curable resin composition may be insufficiently cured. On the other hand, when the accumulated light amount of the lamp exceeds 1,500 mJZ cm ² , This is because the obtained cured coating film may turn yellow and change the hue. Therefore, it is more preferable that the integrated light amount of the lamp when the curable resin composition is radiation-cured is set to a value within the range of 250 to 1, 00 Om JZ cm ² , and 300 to 75. 0 m and even more preferably to a value within the range of JZ cm ^2.

(2) Heat treatment

 Further, it is preferable to perform a heat treatment after the curable resin composition is cured by radiation or before the radiation curing. The reason for this is that by performing such heat treatment, the adhesion between the cured coating film and the aluminum substrate can be further improved.

 The heat treatment conditions are preferably a temperature of 50 to 200 ° C. and a treatment time of 1 to 120 minutes.

3. Aluminum laminate

 (1) Form

 As shown in FIGS. 5 (a) and (b), in the aluminum laminate 30, a cured coating film 12 made of a curable resin composition is formed on the surface of the aluminum base material 10. Is preferred.

 Here, the thickness of the cured coating film is preferably set to a value within the range of 0.001 to 3 mm. The reason for this is that if the thickness of the cured coating is less than 0.001 mm, the adhesion between the cured coating 12 and the aluminum substrate 10 will decrease, This is because the concealing property may be reduced, and further, the mechanical properties and the curing properties of the cured coating film may be reduced. On the other hand, if the thickness of the cured coating film exceeds 3 mm, poor curing may occur or the curing time may be excessively long.

Therefore, the thickness of the cured coating film is more preferably set to a value in the range of 0.005 to 0.5 mm, and in a range of 0.01 to 0.2 mm (10 to 2000 μm). It is more preferable to set the value within. Here, referring to FIG. 6, the effect of the thickness of the cured coating film in the high-concentration white resin composition containing 35% by weight of titanium oxide on the adhesion and hiding properties to the aluminum base material will be described in detail. I do. In Fig. 6, the abscissa indicates the thickness (jum) of the cured coating, and the ordinate indicates the adhesion evaluation (relative value) and the concealment evaluation (relative value) of the obtained cured coating. Shown. Here, the evaluation of adhesion and the evaluation of concealment were performed in the following examples, in which the evaluation ◎ obtained in Example 5 was 5 points, the evaluation 〇 was 3 points, the evaluation was 1 point, the evaluation X was 0 point, and the evaluation was divided. In the evaluation, the average of six evaluation samples was used as the evaluation point.

 As shown in FIG. 6, it can be understood that when the thickness of the cured coating film is within the predetermined range, both the adhesion and the concealing property of the cured coating film are stable. However, when the thickness of the cured coating film is less than 1 m, the concealing property of the cured coating film is reduced. On the other hand, when the thickness of the cured coating film exceeds 50 / m, the adhesiveness of the cured coating film tends to decrease.

 Therefore, in order to improve the adhesion and concealability of the cured coating film and obtain an acceptable evaluation of 1 or more, it is recommended that the thickness of the cured coating film be in the range of 1 to 50 m. In order to obtain a higher evaluation of 3 or more, it is more preferable that the value be in the range of 10 to 25 m.

 The effect of the thickness of the cured coating film applies when rutile-type titanium oxide (high-concentration white) is used as a coloring agent. In the case of a clear or light-colored cured coating film, It is also possible to increase the thickness of the coating.

The form of the aluminum laminate is not particularly limited, but may be, for example, tubular, rectangular parallelepiped, polyhedral, cylindrical, elliptical, spherical, triangular pyramidal, conical, etc. It is preferable to mold it. For example, in the case of a tube-shaped aluminum laminate 30 as shown in FIG. 5 (a), it is assumed that the aluminum laminate 30 is bent or pressed in use, and the present invention has excellent chemical resistance and adhesion. A hard coating with the required cured coating This is an optimal form because it is a laminated laminate.

 In FIG. 5 (a), when the screw portion 31 is made of an aluminum base material, it is preferable that the curable resin composition is also laminated (applied) to the screw portion 31 in order to increase the decorativeness. . On the other hand, in order to strengthen the connection in the screw portion 31, it is preferable not to laminate (apply) the curable resin composition to the screw portion 31.

(2) Painting process

 Further, it is preferable to laminate a paint on the cured coating film that has been cured by radiation. The reason for this is that by performing such a coating treatment, the decorativeness and information of the aluminum laminate can be significantly improved.

 In addition, the radiation-cured cured coating film is characterized by having excellent adhesion to common paints such as acrylic paints, epoxy paints, urethane paints, and polyester paints.

(3) Inner surface treatment

 Further, as shown in FIG. 7, it is preferable to provide an inner resin layer 16 on the aluminum substrate 10 on the side opposite to the surface on which the cured coating film 12 made of the curable resin composition is formed. .

 The reason for this is that, for example, even when the aluminum substrate provided with the resin layer 16 is formed into a tube and the contents are contained therein, the contents and the aluminum substrate 10 are not This is because it is possible to prevent the reaction.

 By providing the resin layer 16 in this manner, the flexibility and mechanical properties of the aluminum laminated body 40 can be significantly improved. Example

[Example 1] 1. Preparation of curable resin composition

 A curable resin composition containing the following components (1) to (4) in a container and uniformly mixing with a stirrer, and having a viscosity of 1, OOO m P a 'sec. It was created. The used epoxy acrylate oligomer containing a polar polar group is referred to as epoxy acrylate oligomer A, and the used urethane acrylate oligomer is referred to as urethane acrylate oligomer A.

 (1) Epoxy acrylate oligomer containing a phosphate group: 100 parts by weight (average molecular weight: 2,000, acid value: 25)

 (2) Urethane acrylate oligomer: 17 parts by weight (average molecular weight: 5,000)

 ③ Acryloyl morpholine: 25 parts by weight

④Isobonyl acrylate: 5 parts by weight

⑤Benzyl dimethyl ketal: 5 parts by weight

⑥Silicone leveling agent: 1 part by weight

⑦ Trimethoxysilane containing vinyl group: 5 parts by weight

チ タ ン Titanium oxide: 35 parts by weight

2. Application of curable resin composition

 Next, the obtained curable resin composition was applied to the surface of a tube made of an annealed aluminum substrate (100 / m in thickness).

 The coating conditions are as follows.

 ①Coating method: Silicone rubber roll coater

 ② Coating speed: 80 tubes

 ③ Set film thickness: 10 to less than 15 jum

3. UV curing of curable resin composition

Next, the curable resin composition on the aluminum tube was cured by ultraviolet rays to form a cured coating film. That is, the aluminum of Example 1 A laminate was made.

 The UV curing conditions were as follows.

 ①Metal halide lamp: 1 lamp, 120WZ cm output

 (2) Distance between lamp and substrate: 100 mm

③ Lamp peak intensity: 670 mWZ cm ²

④ lamp integrated light quantity: 5 0 0 m J cm ²

4. Evaluation

 The ultraviolet curability and stability of the obtained curable resin composition and the cured coating film formed on the aluminum tube were evaluated as follows. The number of samples used for evaluation was 6, and the average of each evaluation was taken as the evaluation result.

 (1) UV curable

 The curable resin composition was ultraviolet-cured while changing the integrated light amount of the lamp, the appearance of the obtained cured coating film was observed, and the ultraviolet curability of the curable resin composition was evaluated based on the following criteria.

◎: No stickiness even with a lamp integrated light amount of 300 mJZ cm ² or less.

0:. Even 5 0 0 m J / cm ² or less lamps integrated light quantity, base backlash no.

Room: 1, OOO m JZ No more stickiness even when the integrated light amount of the lamp is less than ² cm2.

X: 1, 0 0 O m JZ even cm ² a lamp cumulative amount of light beyond the, luck was base there.

(2) Stability

The stability of the curable resin composition was evaluated based on the following criteria from the initial viscosity of the curable resin composition and the change in viscosity over time (room temperature, 168 hours). ◎: Change in viscosity is in the range of 0 to less than 20%.

〇: Change in viscosity is within the range of 20 to less than 50%.

Δ: Change in viscosity is in the range of 50% to less than 100%.

 : The change in viscosity is more than 100%.

(3) Adhesion

 The resulting cured coating film was cross-cut into 100 square grids of 100 squares, and a 24 mm wide adhesive tape manufactured by Nichiban Co., Ltd. was applied. Next, the adhesive tape was peeled off, the number of grids peeled off was measured, and the adhesion of the cured coating film composed of the curable resin composition was evaluated based on the following criteria.

 The number of strips in the grid is zero.

〇: The number of peels in the grid is 1 to 5 pieces.

: The number of strips in the grid is from 6 to 10 pieces.

X: The number of strips in the grid is equal to or greater than 11 pieces in the 100 grid.

(4) Flexibility

 After separating only the body part from the aluminum tube while keeping it cylindrical, a 2 kg weight was dropped on the body part from a height of 450 mm and deformed. Thereafter, the cured film was returned to its original shape, the appearance of the cured film was observed, and the flexibility of the cured film composed of the curable resin composition was evaluated according to the following criteria.

 A: There is no change in the appearance of the cured coating film.

 〇: Slight peeling of the cured coating film is observed.

 Δ: Some cracking of the cured coating film is observed.

 X: Remarkable cracking or peeling of the cured coating film is observed.

(5) Scratch resistance

Clean the surface of the painted aluminum tube with the unpainted aluminum tube. After observing the appearance of the cured coating film after rubbing with a brush, the scratch resistance of the cured coating film was evaluated according to the following criteria.

 A: There is no change in the appearance of the cured coating film.

 〇: Slight scratches and black spots are observed on the cured coating film.

 Δ: Slight scratches / black spots are observed in the cured coating film.

 X: Remarkable scratches / black spots are observed in the cured coating film.

(6) Chemical resistance

By § seton and downy emissions benzyl alcohol soaked cotton wool. The surface of the painted aluminum tube, rubbed 1 0 times under the condition load of about 0. 5 k gZc m ^2. Thereafter, the appearance of the cured coating film was observed, and the chemical resistance of the cured coating film was evaluated according to the following criteria.

A: There is no change in the appearance of the cured coating film.

〇: Slight discoloration of the cured coating film is observed.

Δ: A slight underlayer exposure is observed.

X: Remarkable underlayer exposure is observed.

[Examples 2 to 5]

 The influence of the average molecular weight and the acid value of the epoxy acrylate oligomer was studied.

That is, as shown in Table 1, a curable resin composition was prepared, coated, cured, and evaluated in the same manner as in Example 1 except that the number average molecular weight (Mn) and the acid value of the epoxy acrylate oligomer were changed. Was done.

As a result, for example, the number average molecular weight of the epoxy acrylate oligomer is set to a value in the range of 500 to 10,000, and the acid value of the epoxy acrylate oligomer is set to a value in the range of 5 to 5 Omg KO HZg. As a result, it was confirmed that better adhesion and flexibility of the curable resin composition could be obtained. Jeho. Urethane Clear Latek Link * Agent Dense Ori: Doma Orikoma Wear Soft

ΜΠ mm Addition amount n ¾5 force Priability (mgKOH / g) (SfiSP) (parts by weight).

Example containing vinyl group

 2000 25 100 5000 17

 1 Trimethoxysilane ◎ ◎ Example containing vinyl group

 2000 10 100 5000 17 mm

2 Trimethoxysilane

Example containing vinyl group

 2000 50 100 5000 17

 3 Trimethoxysilane ◎ Δ Example containing vinyl group

 800 25 100 5000 17 Ο ο 4 Trimethoxysilane

Example Containing phenyl group

 800 5 100 5000 17 mm 5 Trimethoxysilane

[Examples 6 to 11]

 The influence of the average molecular weight and the amount of urethane acrylate oligomer was investigated.

That is, as shown in Table 2, a curable resin composition was prepared and evaluated in the same manner as in Example 1 except that the number average molecular weight (Mn) and the amount of the urethane acrylate oligomer were changed.

As a result, for example, the number average molecular weight of the urethane acrylate oligomer was set to a value within a range of 500 to 500, and the amount of the urethane acrylate oligomer was set to 100 parts by weight. Sometimes, it was confirmed that by setting the value within the range of 1 to 50 parts by weight, more excellent flexibility, heat resistance and mechanical properties of the curable resin composition can be obtained. Table 2

[Examples 12 to 14]

 The effect of the type of silane coupling agent was studied. That is, as shown in Table 3, a curable resin composition was prepared and evaluated in the same manner as in Example 1 except that the type of the silane coupling agent was changed.

As a result, for example, when an epoxy acrylate oligomer having a phosphate group is used as the epoxy acrylate oligomer having a polar group, a vinyl group-containing trimethoxysilane or a (meth) acryl group is used as a silane coupling agent. It was confirmed that the use of the trimethoxysilane-containing trimethoxysilane and the ethoxy group-containing trimethoxysilane provided more excellent stability of the curable resin composition. Table 3

[Examples 15 to 17]

 The effect of the thickness of the resulting cured coating was studied. That is, as shown in Table 4, using the curable resin composition of Example 1, the thickness of the obtained cured coating film was changed and evaluated.

As a result, for example, by setting the thickness of the obtained cured coating film to a value within the range of 1 to 5 Oim, it is possible to obtain more excellent concealing property, curability, adhesion, and flexibility of the cured coating film. It was confirmed.

Table 4

産業上の利用可能性

Industrial applicability

 According to the present invention, when producing an aluminum laminate, by providing a laminating step of a specific curable resin composition on an aluminum base material, even if the aluminum laminate is bent, It has become possible to easily and quickly produce an aluminum laminate in which the cured coating film is less likely to peel off.

 Further, in the specific curable resin composition used in the present invention, an appropriate viscosity is obtained due to the excellent compatibility of each component, and a relatively large amount of a concealing agent such as titanium oxide is added. Even in this case, it is possible to effectively prevent excessive sedimentation and poor curing, and to provide an aluminum laminate having excellent concealing properties.

Claims

The scope of the claims 1. A method for producing an aluminum laminate, comprising the following steps (1) and (2).  (1) A step of laminating a curable resin composition containing an epoxy acrylate oligomer having a polar group, an acryl-based monomer, and a curing agent on an aluminum base  (2) a step of curing the curable resin composition by performing radiation irradiation and heat treatment, or one of the curing treatments; 2. When the amount of the epoxy acrylate oligomer having a polar group in the curable resin composition is 100 parts by weight, the amount of the acryl-based monomer is 0.3 to 300 parts by weight. The method for producing an aluminum laminate according to claim 1, wherein the amount of the curing agent is set to a value within a range of 1 to 20 parts by weight. 3. The viscosity (measuring temperature: 25 ° C.) of the curable resin composition is set to a value within a range of 10 to 50, OOO m Pa-sec. 3. The method for producing an aluminum laminate according to paragraph 1 or 2. 4. The method for producing an aluminum laminate according to any one of claims 1 to 3, wherein the curable resin composition further includes a urethane acrylate oligomer. 5. The acrylic monomer in the curable resin composition contains acryloyl morpholine and isobonyl acrylate, or any one of acryl compounds. The method for producing an aluminum laminate according to any one of the above items. 6. The method for producing an aluminum laminate according to any one of claims 1 to 5, wherein the curable resin composition further includes a coupling agent. 7. The aluminum laminate according to any one of claims 1 to 6, wherein the acid value of the epoxy acrylate oligomer is set to a value within a range of 5 to 50 mg KOH g. How to create 8. The polar group in the epoxy acrylate oligomer includes at least one group selected from the group consisting of a carboxyl group, a phosphate group, a sulfonic acid group, and a hydroxyl group. The method for producing an aluminum laminate according to any one of Items 1 to 7, 9. The method for producing an aluminum laminate according to any one of claims 1 to 8, wherein the curable resin composition further includes a coloring agent. 100. A hard coating having a thickness of 0.001 to 3 mm made of a curable resin composition containing an epoxy acrylate oligomer having a polar group, an acrylic monomer, and a curing agent on an aluminum substrate. An aluminum laminate characterized by having a film. 11. The aluminum laminate according to claim 10, wherein the aluminum base is annealed. 12. The surface of the aluminum base material is subjected to at least one surface treatment of ozone treatment, plasma treatment, corona treatment, high-pressure discharge treatment, ultraviolet treatment, and gay acid flame treatment. No. 10 Or the aluminum laminate according to Item 11. 13. The aluminum substrate according to any one of claims 10 to 12, wherein the aluminum base is in a tubular shape, and the cured coating is a concealing coating. Aluminum laminate.