JPS59227445A - 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 having excellent interlayer adhesion, especially durable adhesion, between a metal layer and a modified polyolefin layer.

Conventionally, laminates in which metal layers are laminated on both sides of a polyolefin layer have been used for various purposes such as civil engineering, architecture, furniture, decoration, and automobile articles.

As a method to improve the adhesion between the metal layer and the polyolefin layer of these laminates, for example, a metal foil or metal plate that has been acid-treated with a modified polyolefin in which a polyolefin is reacted with an unsaturated carboxylic acid or a derivative thereof is used. A method of laminating a metal plate, or a method of laminating a metal plate treated with a chemical conversion agent such as zinc phosphate coated with an epoxy primer and a modified polyolefin or polyolefin are known.

However, although the laminates obtained by these methods have high interlayer adhesion, the laminates made with modified polyolefins do not have sufficient durable adhesion such as water resistance and salt water resistance, and the molding temperature is also different. Requires highly targeted conditions.

On the other hand, those using epoxy primers have problems in that the curing time of the primer is long and high temperatures are required, resulting in poor workability and high primer cost.

The present invention aims to improve these problems in the conventionally known laminates consisting of a metal layer and a modified polyolefin layer, and aims to improve adhesive strength and durability even under harsh usage conditions. As a result of research into a laminate that has adhesive strength and can be manufactured with high efficiency, it has been completed.

That is, the present invention provides general formula R1nSi COR2)
<-n [However, R1 is alkyl, cycloalkyl or aryl substituted with a polar group, R2 is alkyl or aryl which may have a substituent, and n = 1 or 2]. The present invention relates to a laminate comprising a metal layer having a polysiloxane film obtained from a compound and a modified polyolefin layer in which part or all of the polyolefin has reacted with an unsaturated carboxylic acid or a derivative thereof.

In the present invention, the organic silane compound represented by the general formula "nSi (OR2) i-n" is an alkyl or cycloalkyl substituted with a polar group having an affinity for an unsaturated carboxylic acid, its acid anhydride, or its esters. Alternatively, R2 is aryl, and R2 is alkyl or aryl which may have a substituent, and examples thereof include n-1 or 2.

Examples of the polar group Rt include amine, ureido,
Examples include chrysitoxy, epoxy, mercapto, and anilino groups. Examples of the substituent for R2 include a methoxy group. Furthermore, examples of the substituent for R2 include a methoxy group.

Specific examples of R1 include γ-aminopropyl, N-β-(aminoethyl λ-γ-aminopropyl,
r-ureidoglobil, r-glycidoxyglobil, β
Examples include -(3,4-epoxycyclohexylene ethyl, paraaminophenyl, r-mercagtoglobil, γ-anilinopropyl, N-β-(N-vinylbenzylaminoethyl-γ-aminopropyl), etc. R2
Specific examples include methyl, ethyl, propyl, butyl, β-methoxyethyl, and phenyl. Preferred examples of these organic alkoxysilanes include γ-aminoglobil trimethoxysilane, γ-
Aminoglobiltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ
-ureidoglobiltriethoxysilane, γ-anilinopropyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-r-aminopropyltrimethoxysilane, and the like. These organic silane compounds can be used alone or in combination of two or more.

The metal layer in the present invention includes aluminum, iron, copper, tin, etc. having a thickness of 1 m or less, preferably 0.02 to 0.5 M,
Metals such as nickel and zinc and one or two of these
Examples include metals whose main component is more than 50% carbon, such as stainless steel. Among these metals, it is preferable to use aluminum instead of iron. Examples of iron include J-K5G-3
Examples include cold-rolled steel plates as defined in 141. These metal layers are used after being pickled, degreased, or chemically treated with zinc phosphate or the like.

In the present invention, a method for producing a metal layer having a polysiloxane film obtained from an organosilane compound represented by the general formula R1nSi (OR2), -n includes, for example, applying a solution of the organosidine compound to the surface of the metal layer. One method is to apply it and dry it.

The organic silane compound solution is prepared by adding the above-mentioned organic silane compound to a solvent, for example, water, alcohols such as methanol, gropanol, and t-butanol, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve, or a mixed solvent thereof. Concentration is 0.05-5.0% by weight
, preferably 0.1 to 2.0% by weight, and the temperature is room temperature to 1.
It can be obtained by uniformly dissolving it under conditions of 00°C, preferably room temperature to 80°C.

Methods for applying this organic silane compound solution include methods such as gravure roll, air spray, spray, roll coater 1 brush, and dipping; however, for continuous application, gravure roll, air spray, Roll coater 1 immersion is preferred. Note that it is preferable that the metal layer to which the organic silane compound is applied is previously subjected to pickling or degreasing treatment.

Furthermore, the organic silane compound solution is dried using a heater, such as a hot air circulation dryer or an induction heater, at a heating temperature of 60 to 250°C, preferably 80 to 200°C, and a heating time of 2 seconds to 10 minutes, preferably. The solvent is removed in 10 seconds to 5 minutes, and silanol condensation is performed to form a polysiloxane film. Note that it is economically preferable that the metal layer, which has been heat-dried to form a polysiloxane film on its surface, is subsequently laminated with a modified polyolefin before being cooled.

The thickness of the polysiloxane film formed on the surface of the metal layer described above can be freely controlled by adjusting the concentration of the organosilane compound and the clearance between the doctor knife installed on the coating roll and the roll, as appropriate depending on the purpose. However, from the viewpoint of the performance of the resulting laminate, it is usually 5μ.
The thickness is preferably below, particularly preferably 1μ or less.

It is not preferable to make the polysiloxane film thicker than necessary because residual strain remains. Furthermore, from an economic standpoint, it is undesirable to make the film thicker than necessary.

Examples of polyolefins used as raw materials for modified polyolefins reacted with unsaturated carboxylic acids or derivatives thereof in the present invention include ethylene, propylene, 1-butene, 1-pentene, S-methy/I/-1-butene, 1-hexene,
A homopolymer of α-olefin such as 4-methyl-1-pentene or a copolymer of one of the above monomers with another α-olefin of 10 molar or less, preferably 7 molar or less, or a mixture thereof. Copolymers of the α-olefins and acyloxy, especially acetoxy-substituted products such as vinyl acetate, or saponified products thereof, and hydrocarbon-based distomers such as polyimbutylene rubber, which have a crystallinity of 20 or more according to analysis. Butyl rubber, ethylene-propylene rubber, ethylene-propylene-
Examples include diene-copolymer, ethylene-1-butene rubber, butadiene rubber, stainless steel-butadiene rubber, and ethylene-butadiene rubber. These polyolefins may be used alone or in mixtures. Among these,
Polyethylene, polypropylene and polyisobutylene rubber, ethylene-propylene rubber, ethylene-
1-butene rubber 1 piece.

Polyolefin blended with butyl rubber is particularly preferred.

As polyethylene, the density is α910~0.960
f/cc, melt index (190℃) is 0.0
5 to 100f/10 minutes is preferable. As the polypropylene, homopolypropylene or random or block copolymer with a melt flow index (230° C. of 0.05 to 10 f1710 min) is preferable.As the polyimbutylene rubber, a homopolymerized density of imbutylene is 0.90 to 0. .93 f/cc, viscosity average molecular weight of I x 106 to I x lo7,
A copolymer rubber of inbutylene and inprene with an isoprene content of 1 to 10% by weight and a Muny viscosity of 10 to 300. A copolymer rubber of isobutylene and chloroprene with a density of 0.90 to α93 f/ca, a chloroprene content of 0.5 to 1% by weight, a Munie viscosity of 10 to 500 at 100°C, and a density of 0. 90-0.
9'6 f/cc is preferred. Ethylene-propylene rubber and ethylene-1-butene rubber,
The ethylene content is 10-90% by weight, and the Mooney viscosity at 100°C is 10-200. Density is 0.85-0.
90f/cc is preferable.

The modified polyolefin in the present invention is produced by graft-modifying part or all of the above polyolefin with an unsaturated carboxylic acid or a derivative thereof. In addition, the modified polyolefins produced include nylon 6, nylon 66, nylon 6.10. It also includes mixtures of nylon such as nylon 12, polyvinyl formal, polyvinyl acetal, polyester elastomer, polyethylene terephthalate, polybutylene terephthalate, and the like.

Examples of unsaturated carboxylic acids or derivatives thereof include acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, endo-bicyclo(2,2 ,1)
-1,4,5,6,7,7-hexachloro-5-hebutene-2,5-dicarboxylic acid, endo-bicyclo(2,
2,+) -j, 4,5.6.7゜7-hexachloro-5-heptene-2,3-dicarboxylic anhydride, endo-
Bicyclo-(2,2,1)-5-hair 'f:/-2,'
5-dicarboxylic acid, endo-bicyclo-(2,2,1
) -5-Hebutene-2,3-dicarboxylic anhydride, cis-4-cyclohexene-1,2 dicarboxylic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, methacrylic acid Butyl, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, monomethyl fumarate, diethyl maleate, diethyl heptamalate, monomethyl itaconate, diethyl itaconate, acrylamide, methacrylamide, maleic monoamide , maleic acid diamide, maleic acid-N-monoethylamide, maleic acid N,
N, diethylamide, maleic acid N.

N dibutylamide, 7malic acid monoamide, fumaric acid diamide, 7malic acid-N-monoethylamide, fumaric acid-N
, N-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, and the like. Among these are maleic anhydride, endo-bicyclo[2,2,1)
-5-hebutene-2,3-dicarboxylic anhydride is particularly preferred.

Various known methods can be used to graft-modify the polyolefin with the monomer of the unsaturated carboxylic acid or its derivative. For example, it is carried out by heating the polyolefin and the graft monomer to a high temperature in the presence or absence of a solvent, with or without the addition of a radical generator. Other vinyl monomers such as styrene and vinylsilane may be present during the reaction. The amount of the graft monomer grafted onto the polyolefin is preferably adjusted to be in the range of 3 to 2% by weight.

The polyolefin may be partially or entirely grafted with an unsaturated carboxylic acid or a derivative thereof, but from the viewpoint of industrial production, it is preferable to set the grafting ratio in advance to 10-3 to 3.
It is preferable to prepare a modified polyolefin in an amount of % by weight and then mix this modified polyolefin with an unmodified polyolefin, since this allows the concentration of the graft monomer in the composition to be appropriately adjusted.

The laminate of the present invention has a basic structure in which a metal layer having a polysiloxane film made of an organic silane compound on the surface and a modified polyolefin layer are laminated to form a metal layer/polysiloxane film/modified polyolefin layer. Therefore, there are no restrictions on the multilayer structure of the laminate as long as it includes such a configuration. For example, a metal layer with a siloxane film that has adhesive properties with modified polyolefin, or synthetic resins such as unmodified polyolefin, polyamide, polyvinyl chloride, polyester, polyurethane, acrylic resin, etc. are used as the core material and exterior material. For example, metal layer/polysiloxane film/modified polyolefin layer/polysiloxane film/metal layer, metal layer/polysiloxane film/modified polyolefin I/core resin layer/modified polyolefin N/polysiloxane film/metal layer Examples include the above-mentioned configuration in which a metal layer/polysiloxane film/modified polyolefin layer/exterior material resin layer or a metal layer having a polysiloxane film is used as a core material.

The above-mentioned method for producing a one-layered product is obtained by supplying a metal layer having a polysiloxane film, a modified polyolefin layer, and a resin layer of a core material or an exterior material continuously or batchwise, and laminating them by heating and pressurizing them. .

As a continuous manufacturing method, for example, a sheet of modified polyolefin in a molten state and two steel plates whose surfaces have been treated with a polysiloxane film are mixed into a sheet of steel plate/polysiloxane film/modified polyolefin layer/polysiloxane film/steel plate. Supplied between heated pressure rollers so that the temperature is 1.
00~250℃, preferably 120~200℃, pressure 0
．． 1~10 Kg/ctr? , preferably 0.4-4K
g/crr? Laminate under the following conditions. In addition, in a batch-type manufacturing method, for example, a sheet of modified polyolefin and two steel plates whose surfaces have been treated with a polysiloxane film are stacked to form a structure of steel plate/polysiloxane film/modified polyolefin layer/polysiloxane film/steel plate. and supplied to a hot press plate at a temperature of 130 to 250°C, preferably 160 to 23°C.
After preheating at 0℃ for 30 seconds to 5 minutes, the temperature is 150 to 250℃.
°C, preferably 160-230 °C, pressure 5-50 Kq
l Vice 2G1 preferably 5-20 Kg/cr111.2
Lamination is performed by pressing for 0 seconds to 5 minutes, preferably 20 seconds to 2 minutes.

It is particularly advantageous for the product of the invention to be manufactured continuously, which will be explained below using the drawings. 1st
The figure is a schematic side view showing an example of an apparatus for manufacturing the laminate of the present invention.

The metal sheet 1 is degreased in advance, then wound into a roll and set in an uncoiler.

It is pulled out from the uncoiler 3 in a stretched state with a constant tension by a take-up roll 4. The tension applied to the metal sheet 1 can be changed arbitrarily by adjusting the braking force of the uncoiler 3, and is usually 0.2 to 0.5 Kg/lar.
Controlled to a constant value within the range of .

The stretched metal sheet 1 is first passed through a gravure roll 6 in an organic silane solution coating step, and the organic silane solution is applied thinly to the metal surface.

The metal sheet 1 is then passed through a preheating step 9, followed by removal of the solvent and formation of a polysiloxane coating. The thickness of the organic siloxane coating film formed is controlled by the concentration of the organic silane solution, the clearance between the doctor knife 7 installed on the gravure roll and the roll A, etc. Although the film thickness can be freely controlled, it is preferably 5 μm or less, particularly preferably 1 μm or less, in view of the performance of the resulting laminate.

The metal sheet on which the preheated and surface-treated coating film has been formed in the preheating process is heated and pressed together with the molten synthetic resin sheet 2 extruded from the extruder 11 before it is cooled.
16, and lamination is performed.

The temperature of the synthetic resin sheet 2 should be determined by considering the wettability between the resin used and the metal, since if it is too low, the resin and the surface-treated metal will not communicate well, and sufficient adhesion to the metal sheet will not occur. If it is necessary to use a modified polyolefin resin, it is best to select a temperature within the range of approximately 170°C to 250°C. If the temperature of the metal sheet 1 is too low, wetting between the resin and the surface-treated metal will be poor, and sufficient adhesion will not be obtained. It is necessary to make a decision by considering the compatibility of the resin and metal used. In particular, it is greatly affected by the characteristics of the resin that is the base of the modified polyolefin, but it is approximately 80℃ ~
It is best to choose from a range of 250°C. Heat pressure bonding roller-1
The temperature in step 3 varies depending on the characteristics of the resin that is the base of the modified polyolefin, the drawing speed of the metal sheet 1, etc.
Although it is not possible to determine the temperature generally, it is preferable to select it from a range of approximately 120°C to 250°C based on the surface temperature of the roll.

The laminated plate sent out from the hot pressure bonding roll 13 is heated and matured in a heating step 14 as necessary, and then cooled in a cooling step 15 to become a product 16.

As described above, the laminate of the present invention has both improved initial adhesiveness and durable adhesiveness, and can be used under severe conditions.

Hereinafter, the laminate of the present invention will be explained in more detail using Examples. In addition, in the examples, ``chi'' indicates weight, and the test method was as follows.

(11 Melt Index (M Engineering) J Engineering S K 67
60(2) Melt flow index (MF en J
Engineering S K 675B (3) Adhesive Strength A test piece of 25 m x 5 DOm was peeled from the end face by 50 m + as a gripping margin, and a 90° peel test was performed at a speed of 10 (1) 7 minutes, and ICn was determined from the adhesive strength.
The adhesive strength of the I width was calculated.

(4) Salt water immersion 50 IIIIIIX 200
A simple test piece at 60℃! Immersion in I%N6C2 solution, 50
After several days, the degree of penetration from the end face was examined.

(5) Heat cycle test 25 am x 5
A test piece of 00 gourd was placed in a constant temperature bath at -30°C for 8 hours, and then heated for 6 hours.
It was set in a constant temperature bath at 0° C. for 16 hours, and this was considered as one cycle. The adhesive strength of the test piece was measured after the same cycle was repeated 10 times.

(6) Post-workability (bending) A test piece of 25 strips x 200 m was wound around the circumference of a 6IIIφ steel bar, and the radius was 5.
A bending process of w+Iφ was performed. The bent portion was cut and the state of peeling was observed.

Example 1 Using the continuous laminate manufacturing apparatus shown in FIG. .2 strips, width 300.) 1 coil 3, an aqueous solution of γ-aminopropyltriethoxysilane with a concentration of 1% is applied to the surface of each laminated layer using a gravure roll 6 at a take-up speed of 5 m/min, and the exit Each steel plate was dried in a steel plate preheating drying device 9 at a temperature of 100°C.Next, each steel plate was treated with this organic silane compound and preheated at a temperature of 90°C.A modified polyethylene [linear low density polyethylene (M process = 2 .0f/
10 minutes, density = 0.926 f/cc, hereafter L
-LDPK-1) 80 parts and ethylene-1-butene rubber (M work = 4.09710 minutes, density = a 88 f/
cc (hereinafter KBR) 25 parts of a modified product obtained by grafting 0.6 g of maleic anhydride to a mixture of 20 parts, L-LDP
Sheet 2 of a composition consisting of 60 parts of K-i and 5 parts of EBR+ was extruded from an extruder 11 with a diameter of 65 mm at a temperature of 2.
Extrusion at 30℃, set temperature 180℃, set pressure 1.0
A laminate 16 was manufactured by heat-pressing with a roll of K17 cm.

The thickness composition of the obtained laminate was: steel plate/modified polyethylene/steel plate force 0.2 m/0.4 vm/(12 m
It was s.

The obtained laminates were subjected to adhesive strength, saline immersion, heat cycle tests, and post-processability (bending) tests, and the results are shown in Table 1.

Examples 2 to 8 Laminated plates were prepared in the same manner as in Example 1, except that instead of an aqueous solution of γ-aminopropyltriethoxysilane with a concentration of 1%, a solution of an organic silane compound as shown in Table 2 was used. The test results are also listed in Table 1.

Comparative Examples 1 to 6 In Example 1, the organosilane compound was not pretreated, and instead of the organosilane compound treatment, zinc syphosphate treatment and cyclomate treatment were performed in advance by a conventional method. A laminate was produced in the same manner except that the temperature at the outlet of the preheating dryer for the steel plate was 160°C and the preheating temperature for the steel plate was 120°C, and the test results are also listed in Table 1. In Example 1, modified polypropylene [crystalline propylene-ethylene block copolymer (MI+'■=i, Of/10 min, ethylene content=
A mixture of 85 parts of ethylene-propylene rubber (MI = 4.01F/10 min, ethylene content = 72%, hereinafter referred to as EPR) + 5 parts of maleic anhydride was added. Modified product 2 grafted with 5%
A laminate was produced in the same manner except that the temperature at the outlet of the preheating dryer for the steel plate was 150°C and the preheating temperature for the steel plate was 140°C. The test results are shown in Table 2.

Example 10 In Example 9, a crystalline propylene-ethylene block copolymer (MFI =
Endobicyclo (2,2,
1) -5-heptene-2,3-dicarboanhydride/acid 0.6
% grafted modified product and 80 parts of PP block-2, the same procedure was carried out except that the temperature at the outlet of the preheating dryer for the steel plate was 160°C, and the preheating temperature for the steel plate was 150°C. A laminate was manufactured and the test results are shown in Table 2.
Also listed.

Example 11 In Example 1, modified nylon [linear low-density polyethylene (M = = s, oy/l) was used instead of modified polyethylene.
Q min, density = α934 t/cc or less L-LDP
K-2) and 50 parts of polyimbutylene (Vistanetx MML-a o (trade name) manufactured by Esso Chemical Co., Ltd.), 40 parts of a modified product obtained by grafting maleic anhydride 06, and crystalline nylon 6 (Unitika Manufactured by: A-1
030BRL (Composition consisting of 60 parts of product name Horn)
A laminate was produced in the same manner except that the temperature at the outlet of the preheating dryer for the steel plate was 180°C and the preheating temperature for the steel plate was 170°C, and the test results are also listed in Table 2.

Comparative Examples 4 to 6 In Examples 9, 10 and 11, no pretreatment of the organosilane compound was performed, and the preheating drying temperature of the steel plate and the preheating temperature of the steel plate were respectively 180°C and +70 t:, (
Comparative Examples 4 and 5) and 200°C and 190°C (Comparative Example 6), but laminated plates were produced in the same manner, and the test results are also listed in Table 2.

Example +2 In Example 1, pure aluminum-based 1100-H24 material (thickness 062 mm, width 50 o=
) was used in the same manner, and the test results are also listed in Table 2.

[Brief explanation of drawings]

FIG. 1 is a schematic side view of a continuous laminate manufacturing apparatus showing an embodiment of the present invention. 1. Metal sheet, 2. Modified polyolefin, 5.
Uncoiler - 14...Take-up roll, 5...Guide roll, 6, 6'...Surface coating device, 7...Doctor knife, 8...Surface coating liquid and container, 9...Preheating drying device, 10...Guide Roll, 11...Extruder, 12...T
-Die, 13...Heat pressure bonding roll, 14...Preheating device,
15...Cooling device, 16...Laminated board agent 1)
Akira agent Ryo Hagiwara −

Claims (1)

[Claims] General formula R1nSi (OR2)4-n (However, R1 is alkyl, cycloalkyl, or aryl substituted with a polar group, R2 has alkyl or aryl that may have a substituent, and n = 1 or 2) A laminate comprising a metal layer having a polysiloxane film obtained from an organosilane compound represented by the formula and a modified polyolefin layer formed by reacting a part or all of a polyolefin with an unsaturated carboxylic acid or a derivative thereof. .