JPS5842451A - Laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminate comprising an aluminum base material coated with an aqueous scission agent. More specifically, the present invention relates to a laminate using an aqueous cysong agent that has excellent adhesion to an aluminum base material and a top coat agent and is excellent in processability.

Aluminum plates or sheets have traditionally been used for various purposes such as nameplates and decorative plates, taking advantage of their excellent properties such as light weight, excellent workability, and beautiful surfaces. In these applications, sizing processing is usually applied to the aluminum surface to prevent scratches on the surface and improve adhesion of ink and paint. Currently, widely used scissors include those based on resins such as polyurethane, epoxymelamine, vinyl, various alkyds, such as short oil, medium oil, and long oil alkyd.
They are used depending on the purpose.

On the other hand, aluminum plates or sheets that have undergone this sizing process are cut or bent before and after the topcoating process of ink, paint, etc., but the processability is poor and cracks may occur in the processed area. , defects such as lifting are likely to occur. Furthermore, the adhesion with ultraviolet curable or electron beam curable inks and paints is very poor.

Furthermore, in recent years, there have been strong social demands for resource saving, energy saving, pollution-free, etc., and there are particularly high expectations for water-based resins. However, thermoplastic aqueous resins such as acrylic and vinyl acetate resins have poor adhesion and water resistance.

Crosslinking may be considered as a means of improving water resistance, but this is not preferable because the adhesiveness is extremely reduced. In other words, the reality is that there is no water-based resin that has excellent processability, adhesion, and water resistance and can be put to practical use. Therefore, it is desired to develop an aqueous sizing agent that has excellent processability such as cutting or bending, adhesion, and water resistance.

Therefore, the present inventors have conducted research on water-based sizing agents that are excellent in processability, adhesion, and water resistance, and have finally arrived at the present invention.

That is, the present invention is a laminate consisting of an aluminum base material, a water-based scissor agent as described below completely applied on the base material, a dried film, and a top coat layer provided on the film.

Aqueous sizing agent: (A) Among the polycarboxylic acid components, it is a dicarboxylic acid containing 0.5 to 10 moles of sulfonic acid metal base with a melting point of 70.
~20011 crystalline polyester resin and/
or (B) 0.5 to 1O of the polycarboxylic acid component
A non-grade polyester resin having a softening point of 40 to 200°C in which molti is a sulfonic acid metal group-containing dicarboxylic acid, a water-soluble organic solvent with a boiling point of 60 to 200°C, and (1
71 water, and (Al, (B), (q and (effect) satisfy the following formulas (1), (2) and (3).

Formula (1): (A)/(B) = 0 to 100/10
0~0 (weight ratio) formula (21: (A)+(B)/(
q/(DI=1~7010~40/20~99 (weight ratio) Formula (3): (O)/(0)+(I)l=O~0
．． 66 (weight ratio) In the present invention, by using the above water-based sizing agent, a laminate with excellent adhesion, processability, and water resistance can be obtained.

Examples of the aluminum base material used in the present invention include untreated aluminum as well as aluminum that has been subjected to various treatments such as hairline processing, sandblasting, alumite treatment, and chemical polishing. The shape of the aluminum base material is generally a flat plate, but is not particularly limited.The top coating agent used in the present invention may include solvent-based, water-based, or photocurable inks such as offset ink, gravure ink, and screen ink. be. In addition, from the viewpoint of protecting the printed surface, a solvent-based Totsuzo coating agent (acrylic, etc.) may be used.
A) sulfonic acid metal base-containing crystalline polyester resin and (B) Su/L.

A stable hydrophobic resin obtained by blending a non-grade polyester resin containing a metal phonate base, (01) a water-soluble organic compound with a boiling point of 60 to 200-0, and (1) water in a specific proportion. This is an aqueous sizing agent.The aqueous sizing agent thus obtained provides a coating film with excellent processability, adhesion and water resistance.

Next, the aqueous scissors used in the present invention will be explained in detail.

In the crystalline or non-grade polyester resin of the present invention, the sulfonic acid metal group-containing aromatic dicarboxylic acid is 0.5 to 10% of the polycarboxylic acid component. Specifically, the polycarboxylic acid component is an aromatic dicarboxylic acid containing no sulfonic acid metal base from 40 to 99.5 mol, an aliphatic or alicyclic dicarginic acid from 59.5 to θ mol, and an aromatic dicarboxylic acid containing a sulfonic acid metal base. It is a polyester resin with a molecular weight of 2.500 to 30.000, consisting of 0.5 to 10 mol of rII, and a polyol component consisting of an aliphatic glycol having 2 to 8 carbon atoms or/and an alicyclic glycol having 6 to 12 carbon atoms. Examples of aromatic dicarboxylic acids containing no sulfonic acid metal group include terephthalic acid, inphthalic acid, orthophthalic acid, and 2,6-s7talenzocarboxylic acid. The aromatic dicarboxylic acid containing no sulfonic acid metal group preferably accounts for 40 to 99.5 moles of the polycarboxylic acid component. If it is less than 40 molti, the mechanical strength and water resistance of the polyester resin will be poor, which is not preferable. 99
．． If the amount exceeds 5 molt, the polyester resin will not be dispersed in the system.

Examples of aliphatic or alicyclic dicarboxylic acids include 3" phosphoric acid/azigic acid, azelaic acid, cefumacic acid, P-decanedioic acid, dimer acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydrophthalic acid, and hexahydrophthalic acid. Acids, hexahigh V lotylephthalic acid, etc. The aliphatic or alicyclic dicarboxylic acid is preferably 59.5 to 0 mol of the polycarboxylic acid component. 59.
If it exceeds 5 molt, water resistance and coating strength will decrease and tackiness will appear. Zurani P-hydroxybenzoic acid, P-(
(2-hydroxyethoxy)benzoic acid or hydroxypiparic acid, γ-butyrolactone, ε-caprolactone, etc. can be used as necessary. Further, if necessary, a trifunctional or higher functional polycarzanoic acid such as trimellitic acid or gyromellitic acid can be used as long as it is not more than 10 molti based on the total polycarboxylic acid components.

Propanediol, 1,4-butanediol, neopentyl glycol, 1,5-bentanediol.

Examples include diethylene glycol and 1,6-hexanediol. Examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol. The amount of aliphatic glycol having 2 to 8 carbon atoms and/or alicyclic glycol having 6 to 12 carbon atoms is 90 to 100 molti based on the total polyol component. Further, if necessary, a trifunctional or higher functional polyol such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, etc. may be used in an amount of 10 mol or less based on the total polyol component. Furthermore, the molecular weight is 500 to 5.000.
If necessary, polyzolopylene glycol or polytetramethylene glycol may be used in an amount of 40% by weight or less based on the total polyol component, and the molecular weight is 150 to 1.
0,000 polyethylene glycol can also be used in an amount of 20% by weight or less, preferably 10% by weight or less based on the total polyol component.

Examples of the aromatic dicarboxylic acids containing sulfonic acid metal bases include sulfoterephthalic acid, 5-sulfoinphthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5[4-sulfophenoxycoinphthalic acid]. Metal salts can be given. Metal salts include Li, N
Examples include salts such as B, K, Mg, ell, Ou, and Fe. Particularly preferred are 5-sodium sulfoiphthalic acid and 5-potassium sulfoiphthalic acid. The aromatic dicarboxylic acid containing a sulfonic acid metal group is 0.5 to 10 mole based on the total polycarboxylic acid component,
Preferably, the amount is in the range of 1 to 7 mole based on the total polycarboxylic acid component. When no sulfonic acid metal group-containing aromatic dicarboxylic acid is used, the polyester resin has very poor dispersibility in water. As the amount of the metal base-containing aromatic zocarzanoic acid increases, better dispersibility is exhibited. However, if the amount exceeds 10 molt, the resulting polyester resin will have good dispersibility in water, but the water resistance of the film obtained after applying and drying will not only be very poor, but also have poor adhesion. Sexuality also becomes inferior.

The crystalline polyester resin of the present invention has a melting point of 70 to 200
℃, particularly preferably 90 to 180'O.

If the melting point of the crystalline polyester resin is less than 70° C., the resulting coating will have insufficient water resistance.

On the other hand, if the melting point exceeds 200°C, the dispersibility in water becomes poor.

The crystalline polyester resin in the present invention is 50 d or more,
Desirably, it is necessary to have a heat of crystal fusion of Zoo-1,500 m, and if the heat of crystal fusion is less than 50 d, water resistance, especially hot water resistance, will be poor.

The non-grade polyester resin of the present invention has a softening point of 40 to 20.
0°C, preferably 60-180"C.

10 where the softening point of non-grade polyester resin is less than 40゛0
- If the temperature exceeds ℃, the dispersibility in water becomes poor.

The molecular weight of the crystalline or non-crystalline polyester resin of the present invention is from 2,500 to 30,000, preferably from 0.000 to 0.2
It is 0,000. The molecular weight of polyester resin is 2.5
If it is less than 00, not only the water resistance is insufficient, but also the adhesion and processability are poor. On the other hand, the molecular weight is 30.0O
If Oi is exceeded, the dispersibility in water becomes poor.

The water-soluble organic compound used in the present invention is
Solubility in water is 201? Examples of the above organic compounds include aliphatic and alicyclic alcohols, ethers, esters, oyohiketone compounds, and the like. Specifically, for example, methanol, ethanol, n-7' lovanol, iso--f' lovanol, n-butanol, 1so-butanol, 5ee-butanol, tert
- Monohydric alcohols such as butanol, glycols such as ethylene glycol and propylene glycol, methyl cellosolve, ethyl selon, inderovir selon, tert-butyl selon, n-butyl selon, 3-methyl-3-methoxybutanol, These include glycol derivatives such as n-butylseron rubacetate, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate, and ketones such as methyl ethyl ketone, cyclohexanone, cyclooctanone, cyclodecanone, and inholone. Particularly preferred are n-butylseronlube, tert-butylseronlube, inzoloparselonlube, ethylseronlube, inzolopanol and the like. These water-soluble organic compounds can be used alone or in combination of two or more. It is necessary that the boiling point of these water-soluble organic compounds is in the range of 60 to 200''C.

If the boiling point does not reach 60°C, it is difficult to maintain a temperature sufficient to mix or dissolve the polyester resin in the organic compound. If the boiling point exceeds 200°C, the aqueous cysong agent obtained will not dry quickly after being applied.

The aqueous scissor agent in the present invention is prepared by mixing (A) a crystalline polyester resin, (b) a non-grade polyester resin, and (q) a water-soluble organic compound in advance at 50 to 200°C,
It is produced by adding water to this or adding a mixture of (A) and (q) to water and stirring at 40-120"C. Alternatively, (D!1 water and ρ) a water-soluble organic It can also be produced by adding the polyester resins (A) and (B) into a mixed solution with the compound and stirring and dispersing the resin at 40 to 100°C.

In both methods, the blending ratio of (A) crystalline polyester resin, (B) non-grade polyester resin, (q water-soluble polymer compound, and (Di water) is important in maintaining the performance of the water-based scissor agent. It is necessary to satisfy the mixing ratios of formulas 1), 2), and 3).

Formula (1) (A)/(B)=O~Zoo/100~
0 (weight ratio) formula (2) (A) + (11)/(0)/
(DI=1.0~7010~40/20~99 (weight ratio) Formula (3') ((E)/(0)+ (S=θ~0.6
6 (weight ratio) Polyester resin 1d contained in the aqueous dispersion (A) Both a crystalline polyester resin and (very) non-quality polyester resin may be contained, and each may be used alone.

If the blending ratio of (A) crystalline polyester resin and/or (B) non-grade polyester resin contained in the aqueous cysong agent does not reach more than 1.0% by weight, and if the tfC exceeds 70% by weight, the aqueous scythong agent The viscosity becomes too low or too high, which is undesirable. Contained in water-based sizing agent
(0) If the blending ratio of the water-soluble organic compound exceeds 40 parts by weight, the drying property will deteriorate, which is not preferable. Especially preferably (
q The blending ratio of water-soluble organic compounds is Fiso weight % or less.

The aqueous scission agent of the present invention can be used as it is, but it can also be used with one or more compounds selected from the group of amino resins, epoxy compounds, and incyanate compounds as crosslinking agents.

Examples of the amino resin include urea, melamine, formaldehyde adducts such as guanamine, and alcohols having 1 to 6 carbon atoms. Alkylated products can be mentioned. Further, if necessary, a desirable effect can be achieved by using formalin in combination.

Epoxy compounds include bisphenol A diglycidyl ether and its oligomer, hydrogenated bisphenol A diglycidyl ether and its oligomer, orunphthalic acid diglycidyl ester, inphthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid. Acid glycidyl ester ether, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid zoglycidyl ester, cono-lyric acid diglycidyl ester, azigic acid diglycidyl ester,
Sepacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanethiol zoglycidyl ether and polyalkylene glycol diglycidyl ethers, trimeritic acid Acid triglycidyl sol ester, triglycidyl in cyanurate, 1,4-diglycidyloxybenzene, diglycidyl dimethylhydantoin, diglycidyl ethylene urea, diglycidyl pyrene urea,
Examples include glycerol polyglycidyl ether, trimethylolethane polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and polyglycidyl ether of glycerol alkylene oxy-P adduct.

Furthermore, the incyanate compound may be aromatic, aliphatic, or araliphatic diincyanate, trivalent or higher polyincyanate, a low molecular compound, or a polymer compound. Cyanate, hexamethylene diincyanate, toluene diincyanate, diphenylmethane diincyanate, hydrogenated diphenylmethane diincyanate, xylylene diincyanate, hydrogenated xylylene diincyanate,
Incyanate compounds such as inphorone diincyanate, trimers of inphorone diincyanate, or excess amounts of these incyanate compounds, such as ethylene glycol, brolene gellicol, trimethylolpropane, glycerin, nrubitol, ethylene glycol, etc. A compound obtained by reacting with a low-molecular active hydrogen compound such as amine, monoethanolamine, jetanolamine, triethanolamine, etc. or a high-molecular active hydrogen compound such as various polyether polyols, polyester polyols, polyamides, etc. Examples include compounds containing a terminal incyanate group.

The incyanate compound may be a blocked incyanate. Examples of the incyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, ethylphenol, fre-to-rucinol, xylenol, thi-rucinol, nitrophenol, and chlorophenol, acetoxime, methylethylketoxime, and cyclohexanone. Oximes such as oxime, alcohols such as methanol, ethanol, propatool, butanol, ethylene chlorohydrin,
17-halogen-substituted alcohols such as , β-propyl dicutam, and other lactams, as well as aromatic amines, imides, acetylacetone, acetoacetate, malonic acid ethyl ester, and other active methylene compounds, mercaptans, imines, and ureas. , sialyl compounds, sodium bifa acid, and the like. The blocked incyanate can be obtained by addition-reacting the above-mentioned incyanate compound with an incyanate blocking agent by any conventionally known appropriate method.

A curing agent or an accelerator may also be used in combination with these crosslinking agents. 8 Methods of blending crosslinking agents include (A) mixing with crystalline polyester resin or Fi (B) non-grade polyester resin, direct water-based There are methods such as adding it to a sizing agent, and dissolving or dispersing it in a mixture with a water-soluble organic compound or water in advance.
It can be selected arbitrarily depending on the type of crosslinking agent.

The aqueous scissor agent of the present invention has unprecedented processability and
It exhibits adhesion and water resistance. The aqueous sizing agent of the present invention may contain pigments, dyes, various additives, and the like.

The laminate of the present invention is usually obtained by coating the aqueous sizing agent on an aluminum base material and drying it to obtain a film, and then applying a top coat onto the film and drying it. The aqueous cysong agent layer and topcoat layer may be provided simultaneously.

A roll coater is usually used to apply the aqueous cysong agent and topcoat. It may also be applied by screen printing.

In addition, the drying method for the aqueous sizing agent and topcoat agent is air drying or forced drying (for example, at 70°C for 10 minutes, io
2 minutes at 0°C, 1 minute at 150-0, etc., and 5-30 minutes at 100-200°C for baking type. )and so on.

Furthermore, after applying a sizing agent to the aluminum base material, processing such as bending may be performed, and the laminate of the present invention can improve adhesion to the base material and improve workability by using the above-mentioned water-based sizing agent. It has excellent water resistance and is used for various purposes.

EXAMPLES The present invention will be explained in detail below with reference to Examples, but the present invention is not limited to these Examples.

In the examples, parts simply indicate parts by weight.

Evaluation of various properties was performed according to the following methods.

l) Molecular weight Measured using a molecular weight measuring device (Model 115 manufactured by Hitachi, Ltd.).

2) Crystal melting point and crystal melting temperature using a differential scanning calorimeter (manufactured by Takashi Seisakusho) to determine the heating rate lO
Measured at °C/min.

3) Softening point fully automatic melting point measuring device rMETTLEI (manufactured by MUDE)
LFP-1) was used for measurement.

4) Particle size of aqueous dispersion Measured using a grindmeter and an optical microscope.

5) Adhesion Compliant with ITM-3359.

6) Water resistance Compliant with JI" 5400.

7) Hardness of film Compliant with JII'l K 5400.

8) Workability When bending a painted aluminum plate by 180 degrees, insert an untreated aluminum plate and process it, and determine the workability by the number of untreated aluminum plates when lifting or cracking occurs in the processed area. evaluated.

Example: 5T means that if 5 untreated aluminum plates are inserted, there will be no cracks or floats in the processed area, but if 4 plates are inserted, cracks or floats will occur.

OT means that even if untreated aluminum plates are processed without being inserted, no cracks or lifting will occur.

Production Example 1 475 parts of dimethyl terephthalate, 466 parts of dimethyl inphthalate, 45 parts of 5-sodium sulfoi-21-zomethyl sophthalate, 443 parts of ethylene glycol
parts, neopentyl glycol 400 parts, zinc acetate 0.4 parts
4 parts, 0.05 parts of sodium acetate, and 0.43 parts of antimony trioxide were charged into a reaction vessel, and the temperature was increased to 140"C~220
The transesterification reaction was carried out over a period of 4 hours at 260°C.Then, while increasing the temperature to 260°C, the pressure inside the reaction system was frequently reduced to 1c 5711nHg after 1 hour.
A polycondensation reaction was carried out for 1 hour at 60° C. under a reduced pressure of 0.3 ffjlHg, and the molecular weight was 7.000 and the softening point was 152.
A non-quality polyester resin ('A-3) of '0 was obtained.

As a result of composition analysis such as NMR, polyester resin rA
The composition of -3) was 49 moles of telental acid, 48 moles of inphthalic acid, 3 moles of 5-sodium sulfoiphthalate, and 5 moles of ethylene glycol. Further, the heat of crystal fusion of the polyester resin was measured using a differential scanning calorimeter, but no equivalent endothermic peak was observed.

Furthermore, a non-grade polyester resin ('A
-2) to ('&, -7), crystalline polyester resin rB-t), and (B-2) were obtained. Their characteristic values are the first
It was as shown in Tables-1 and -2.

Table 1-1 @ Table 1-2 Example 1゜Non-quality polyester resin rA-t) too part and n-
After about 3 hours of stirring at 130°C for about 3 hours, 360 parts of water was gradually added while stirring, and after about 1 hour, a homogeneous pale bluish-white mixture was obtained. An aqueous sizing agent (1) was obtained.

The resulting aqueous cysong agent was coated onto an untreated aluminum plate with a thickness of 1.01 EI using a bar coater IO to give a solid film thickness of 1.0 μm, and then dried at 100° C. for 5 minutes. The obtained film had good adhesion and processability, and showed water resistance without whitening even after being immersed in water for 7 days. When printing with ink, the adhesion of red and black inks is 100/100,
It was very good.

Examples 2 to 4, Comparative Examples 1 to 4 Aqueous scissors (It) to OV) were obtained in the same manner as in Example 1 using the formulations shown in Table 2. Table 3 shows the performance of the films obtained from these aqueous sizing agents (It) to (g). Table 3 shows the performance of the films obtained with V~■), 25-0, and f'.

26- Example 5 The same procedure as in Example 1 was carried out except that 100 parts of aqueous scission agent (T) and 5 parts of amino resin and Sumimaru M-30W (manufactured by Sumitomo Chemical Industries, Ltd.) were mixed uniformly. A film was formed on an untreated aluminum plate. The performance of the obtained film is shown in Table 4.

Comparative Example 5゜Instead of the aqueous sizing agent (1), an aqueous sizing agent (
Vl)'ff: A film was obtained on an untreated aluminum plate in the same manner as in Example 5 except for using. The performance of the obtained film is shown in Table 4.

Table 4 [*] Immediately before measuring adhesion, water on the surface was wiped off with gauze.

29- Comparative Example 6 Aqueous sizing agent (instead of D, epoxy melamine solvent-based sizing agent, R-77-600 (manufactured by Toyo Ink)
A coating film was obtained on an untreated aluminum plate in the same manner as in Example 5, except that a coating film was obtained on an untreated aluminum plate. The performance of the obtained film is as follows Table 5 C*) Sunshine Unizu Off-ter The adhesion after 100 hours and 300 hours test was evaluated.0 Patent Applicant: Toyobo Co., Ltd. 30-

Claims (1)

[Scope of Claims] A laminate consisting of an aluminum base material, a film obtained by coating and drying the water-based scissor agent described below on the base material, and a top coat layer provided on the film. Aqueous cysong agent: (A) 0.5 to 10 mol of the polycarboxylic acid component is dicarboxylic acid containing sulfonic acid metal base, melting point 70
Crystalline polyester resin having a softening point of ~200°C and/or (in which 0.5 to 10 mole of the homogeneous polycarboxylic acid component is dicarboxylic acid containing metal sulfonic acid groups) Quality polyester resin and 0
contains a water-soluble organic solvent (boiling point 60 to 200°C) and (D) water, and (A), (B), 0 and p) are represented by the following formula (
1), (2) and (3) are satisfied. Formula (1): (A)/[B)=0-Zoo/100~
0 (weight ratio) formula (31: 0/(0)+[F]=θ
~0.66 (weight ratio)