JP2528835B2 - Heated / pressurized compression laminated product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a compaction (consolidat) by heating and pressing having a plurality of core sheets impregnated with a polyester resin.
e) the decorative laminated product.

[Conventional technology]

Decorative laminates compressed by heat and pressure generally include sheets of crust paper impregnated with phenolic resin, topsheet impregnated with melamine / formaldehyde resin, and optionally an overlay impregnated with melamine resin. It is manufactured using a core material including a sheet.

Examples of these high pressure laminates are found in Grosheim et al.
et al., U.S. Pat. No. 3,418,189, Casey et al.
y el al.) U.S. Pat. No. 4,311,748 and Jaisle et al. U.S. Pat. No. 4,473,613, which are used worldwide as building materials, such as wallboards and counter decks in homes and offices. Is accepted. The high-pressure laminate can be manufactured to function according to various uses, and can be manufactured to have a surface with high gloss, matte finish or embossed finish.

In recent years, decorative laminates having a core sheet impregnated with melamine formaldehyde have been able to match the core with the surface or with the decorative sheet, and darker edge lines found when cutting or processing conventional laminates. It was proposed because there is no. However, this core and decorative sheet color matching was achieved at the expense of flexibility. In this regard, Keeling et al.
U.S. Pat.No. 4,448,849 to Hydroxylamine-containing melamine for the purpose of impregnating core sheets and / or decorative sheets and / or overlay sheets to give laminates an inner color edge that matches the color of the core surface. -Showed to use formaldehyde resin. This laminate was capable of secondary molding but did not have the required flexibility.

[Problems to be solved by the invention]

It is an object of the present invention to provide a heat and pressure compressed decorative laminate having a core color that matches the decorative sheet and has increased flexibility.

Another object of the invention is to provide flexibility to the surface sheet and compression laminate impregnated with the thermosetting melamine / formaldehyde reaction product, while the core is intimately colored to the surface sheet and / or backsheet of the laminate. And a core made of a plurality of core sheets impregnated with an unsaturated polyester having an acid value of 90 or less so that the above can be combined with each other.

[Means for solving problems]

According to the present invention, one or more core sheets impregnated with a composition for treating a core sheet containing an unsaturated polyester having an acid value of 90 or less in order to impart flexibility to a laminate, optionally a melamine / formaldehyde reaction Product-impregnated backsheets, topsheets, coresheets and optional backsheets are laminates that have improved flexibility and are resistant to chipping and are easy to process and High pressure decorative laminate having a surface sheet impregnated with a thermosetting melamine / formaldehyde reaction product, characterized in that the color has been compressed by heat and pressure to match the color of the surface and backsheet Will be provided with goods.

Further, according to the present invention, a core product is formed by stacking a plurality of resin-impregnated paper core sheets, a resin-impregnated topsheet, and optionally a resin-impregnated backsheet to form a laminated sheet assembly. One or both of the impregnating agent and, if desired, the topsheet and the backsheet, is an unsaturated polyester with an oxidation of 90 or less in order to give flexibility to the compression laminate. Provided.

The present invention preferably comprises (a) a surface sheet impregnated with a thermosetting melamine / formaldehyde reaction product, (b) two or more colored core sheets, each core sheet having an acid value of 90 or less. Saturated polyester, contact to further polymerize the polyester to make it thermosetting, impregnated core sheet treated to contain 20 to 70 wt% of resin, and impregnated to dry to contain 1 to 5 wt% of volatile components. A core sheet, (c) a back sheet optionally impregnated with a thermosetting melamine / formaldehyde reaction product, the resulting compression laminate has improved flexibility by packaging tests at room temperature, ie The resulting laminate can wrap a diameter of 7.62 to 12.7 cm (3 to 5 inches), while the core sheet produces a melamine / formaldehyde reaction product. The diameter of the laminated product impregnated with material is 12.7 to 15.24c.
Provided is a heated, pressure-compressed laminate which can only wrap m (5-6 inches).

The present invention also provides, according to another embodiment, (a) a topsheet impregnated with a polyester resin, (b) an unsaturated polyester having an oxidation of about 90 or less and a solvent for the polyester for imparting flexibility to a compression laminate. A plurality of core sheets impregnated with the composition containing (c) a backsheet optionally impregnated with a melamine / formaldehyde reaction product, a topsheet (a), a coresheet (b) and an optional backsheet (c) ) Has improved flexibility, is resistant to chipping, and is easy to machine,
Provided is a heat and pressure compression laminate which is heat and pressure compressed to provide a laminate having a core sheet of a color that matches the color of the surface and backsheet.

Generally, according to the present invention, the core sheet is made by impregnating cellulosic paper colored in a color that matches the color of the top sheet, and the top and back sheets optionally include pigments, prints, patterns or designs. Produced by impregnating alpha cellulose paper.

Typically about 278.7 m ² (3000 ft ² ) per ream
27.2 kg (60 lbs) to about 72.6 kg (160 lbs) basis weight (bas
is weight) paper is used for the core sheet, and the alpha cellulose paper used in the surface layer is about 18.1 kg (40 lbs) to 54.4 kg (120 lbs) per 278.7 m ² (3000 ft ² ).
Generally operated on basis weight. The core sheet may comprise several saturated grades of paper, such as alpha-cellulose, bleached kraft or cotton linters, and such papers may be colored to suit the decor or facesheet.

In general, unsaturated polyesters for core sheets that provide flexibility to the laminate are polyhydric alcohols, saturated dicarboxylic acids, and unsaturated polyesters that are reaction products of unsaturated dicarboxylic acids, preferably propylene. Manufactured from glycol, isophthalic acid and maleic anhydride. As is known, the acid component is generally used in an amount of about 1.0 to 1.05 mol per mol of glycol.

The brown-black to black phenolic resins affect the color of the colored core sheet, whereas the unsaturated polyesters used in the present invention do not. Also, the color is more stable than phenolic resins for substantially longer periods.

Also, unsaturated polyesters include propylene glycol, maleic anhydride and recycled polyethylene terephthalate (PE
T) resins; can be made from regenerated products, for example from carbonated beverage bottles. As is known, in the production of impregnated core sheets, catalysts are used to further polymerize the unsaturated polyester. The catalyst is capable of releasing free radicals such as organic peroxides and inorganic persulfates, and is preferably t-butyl perbenzoate. The treatment solution for impregnating the core sheet with the unsaturated polyester includes
Vinyl, acrylic or allylic monomers such as styrene, methyl methacrylate and diallyl phthalate can be used as crosslinking monomers.

The acid value of the unsaturated polyester is generally 90 or less, preferably about 10 or 15 to about 50 or 60, more preferably about 18 or 20 to about 23 or 25. Excellent results have been obtained with an acid number of about 20. In particular, it is obtained for the polyesters produced from propylene glycol, isophthalic acid and maleic acid, and such preferred polyesters are about 4.5-6.
5 minutes, about 1 Brookfield viscosity at 25 ° C
It showed 4 to 17 g / cm · sec (poise) (in 60 / 40-styrene).

Generally, the reaction composition for impregnating each core layer comprises about 30-60 parts by weight of the polyester, about 30-60 parts by weight of acetone or other solvent for the polyester, about 1 part.
Alternatively, 2 to 8 or 10 wt% t-butyl perbenzoate or other catalyst is included to further polymerize the polyester and, if desired, about 1 to 70 wt% of a crosslinking monomer such as styrene. Preferably, the treating solution comprises about equal parts by weight of acetone and the polyester, about 4 wt% t-butyl perbenzoate based on the weight of the polyester, and about 5 parts by weight of the crosslinking monomer when used. ~ 15
wt%.

The core sheet impregnated with unsaturated polyester provides the resulting compression laminate with much improved flexibility.

The laminate is sufficiently flexible that the core sheet impregnated with the melamine / formaldehyde reaction product can only wrap between 12.7 and 15.24 cm (5-6 inches) in diameter, whereas the laminate is much more flexible. It is flexible enough to wrap 7.62 to 12.7 cm (3 to 5 inches) without breaking at room temperature.

Compositions treated with the polyester are generally about 20% solids.
~ 80 wt% solution, the preferred amount is about 40-60 wt%, the optimal amount is about 45-50 wt%.

For impregnating topsheets, thermosetting, as is known in the art, is an initial condensate generally prepared from about 1.0 to 2.7 moles formaldehyde per mole melamine, preferably about 1.75 to 2.25 moles. A melamine / formaldehyde reaction product is used. If desired, small amounts of modifiers can be used, such as about 1 to 20 wt% based on the weight of the reaction product, such modifiers including dicyandiamide, ortho-para-toluenesulfonamide, Sucrose and glycols such as diethylene glycol are included.

As mentioned above, the topsheet can be impregnated with a polyester resin, preferably the same unsaturated polyester impregnation used for the core sheet impregnation.

Disadvantageously, in some cases, even the face sheet or even the core sheet, Richardson
A resin system which is a mixture of melamine (about 15-25 wt%) and polyester resin (about 75-85 wt%) can be used for impregnation, as described in US Pat. No. 2,809,911. The Richardson patent does not mention melamine / formaldehyde printed topsheets, and the structure of the Richardson patent and the laminate according to the present invention are characterized by the nature and structure of the polyester molecules used, the core resin content, the treatment method and the drying. They are dissimilar in time, lamination pressure and structure of the laminate.

In producing the multi-resin system decorative laminate of the present invention, excellent results were obtained as follows. About 5
~ 9, preferably 6 or 7 core sheets are impregnated with the unsaturated polyester treating solution to a resin content of about 38-42.
wt% and then 82.22 ° C to 104.44 ° C so that the volatile components are generally about 1.5-4 wt%, preferably about 2 or 3.5 wt%.
Dry at (180 ° F-220 ° F).

The resulting laminate generally has a thickness of 0.127-
0.178 cm (0.05-0.07 inch), with improved flexibility, good color, chipping resistance, punching processability, normal stain resistance, scratch resistance, surface abrasion resistance, etc. In addition to that, it has favorable characteristics that it is easy to handle and process.

According to a preferred process for producing the laminate of the invention, after at least partial drying, the impregnated sheets are stacked in the required number and arrangement and the stack is placed between stainless steel pressure plates. If desired, a textured sheet can be used between the topsheet and a plate to impart gloss and texture to the topsheet.
The texture sheet is removed after processing. Then about 115.
Approximately 56.2 at temperatures of 56 ° C to 176.67 ° C (240 ° F to 350 ° F)
5kg / cm ^{2 to} 98.43kg / cm ² (800 to 1400psi) pressure, 20 to
It is pressed for 90 minutes and cured to produce a high pressure decorative laminate.

The present invention is illustrated by the following examples, which are not meant to be limiting in any way.

〔Example〕

Prints or facesheets were prepared by treating one roll of pigmented alpha-cellulose decorative paper with the melamine / formaldehyde reaction product. The paper used had a basis weight of 31.3 kg (69 lbs) per 278.7 m ² (3000 FT ² ). The melamine / formaldehyde reaction product reacts 2.0 mol of formaldehyde per 1 mol of melamine to give 2 wt of dicyandiamide as a modifier.
% Was added to manufacture.

Pass the web of paper through the resin-filled dip stack and send it to the sky roll to improve the permeability.
It was passed through a squeeze roll to reach 55%. The web was dried in a treater oven to a volatile content of 5% and cut into regular length sheets from the web.

Unsaturated polyester impregnated core sheet, basis weight 278.7m ²
97 rolls of 44.0 kg (97 lbs) per (3000 FT ² ) of pigmented alpha cellulose were prepared by treating them in polyester resin. The resin was produced by reacting propylene glycol, isophthalic acid and maleic acid in order to adjust the acid value of polyester to 20. The polyester resin was prepared by diluting a solution containing 50% solids with acetone as a solvent, and adding 4% t-butyl perbenzoate as a catalyst to the polyester. The unsaturated polyester resin solution is as follows.

Polyester Resin Solution 45.4 kg (100 lbs) Polyester 45.4 kg (100 lbs) Acetone 1.8 kg (4 lbs) t-Butyl Perbenzoate Alpha-cellulose paper web is passed through a dipping tank filled with polyester resin The tree content
It was passed through a Mayer rod to reach 40%. The web was dried to a volatile content of 2% and cut into sheet lengths corresponding to print sheets.

An internal color laminate was made by assembling the component sheets described below.

1. Textured paper (alpha-cellulose paper filled with clay) 1. Melamine-treated print sheet (top sheet) 6. Polyester-treated core sheet 1. Melamine-treated print sheet (back sheet) , 140.56 ℃
It was compressed with a hydraulic press at a pressure of 84.37 kg / cm ² (1200 psi) at a temperature of (285 ° F.). After pressing, the textured paper was removed and the laminate was cut and finished with a sadder.

〔The invention's effect〕

The resulting compression laminate is a NEMA standard (NEMA is National Electrical Manufacturers' As
abbreviation for sociation).

The resulting laminate was resistant to chipping, was easily processable, and had a core sheet color that matched the surface and backsheet. The laminate was flexible as evidenced by packaging tests at room temperature and packaged diameters of 7.62 cm to 12.7 cm (3 to 5 inches).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-122149 (JP, A) JP-A-59-158250 (JP, A) JP-B-44-11020 (JP, B1) JP-A-56- 500607 (JP, A)

Claims (11)

(57) [Claims] 1. A surface sheet impregnated with a thermosetting melamine / formaldehyde reaction product under heat and pressure; (b) impregnated with a composition containing an unsaturated polyester having an acid value of 90 or less. One or more core sheets;
And (c) A laminate for high-pressure decoration obtained by pressing a back sheet impregnated with a melamine / formaldehyde reaction product, if desired, wherein the pressing is performed for 20 to 90 minutes at 115.6 ° C to 176.7 ° C (240 ° C). F ~ 3
56.25kg / cm ² ~ 98.43kg / cm ² (800psi ~ at a temperature of 50 ° F)
1400 psi) to provide a laminate having improved flexibility and chipping resistance and having a core sheet color intimately matched to the surface and back sheet colors. 2. A laminate according to claim 1 wherein the core sheet (b) comprises two or more sheets treated with unsaturated polyester. 3. The laminate according to claim 1 or 2, wherein the unsaturated polyester is a reaction product of a polyhydric alcohol, a saturated dicarboxylic acid and an unsaturated dicarboxylic acid. 4. An unsaturated polyester prepared from propylene glycol, isophthalic acid and maleic acid, said unsaturated polyester having a typical acid number of 20 and having a SPI gel test at 80 ° C. in about 4.5 minutes to 6.5 minutes. Yes, with a Brookfield viscosity at 25 ° C of about 14-17g /
The laminated product according to claim (3), which has a cm · sec (poise) (in 60/40 styrene). 5. The laminated product according to claim (1) or (2), wherein the unsaturated polyester is produced from propylene glycol, isophthalic acid and maleic anhydride. 6. The composition according to claim 1, wherein the composition for treating a core sheet contains a catalyst for further polymerizing an unsaturated polyester, and the catalyst is effective for releasing a radical polymerization initiator. The laminated product according to any one of item (5). 7. A composition for treating a core sheet comprises the same weight of acetone and an unsaturated polyester having an acid value of about 20, wherein the composition comprises about 4% of perbenzoic acid based on the weight of the polyester.
A laminate according to claim 6 comprising t-butyl and optionally 1 to 70% by weight of the polyester of a crosslinkable monomer. 8. The laminate according to any one of claims (1) to (7), wherein the composition for treating a core sheet contains a vinyl, acrylic or allylic crosslinking monomer. 9. The laminated product according to claim 1, wherein the composition for treating a core sheet is a solution having a solid content of 20 to 80% by weight. 10. The melamine / formaldehyde reaction product optionally comprises dicyandiamide as a modifier.
The laminate according to any one of claims (1) to (9), which is an initial condensate produced from 1.0 to 2.7 mol of formaldehyde per mol of melamine. 11. A surface sheet impregnated with a thermosetting melamine / formaldehyde reaction product under heat and pressure; (b) two or more colored core sheets, each core sheet having an acid value of 90. Impregnated with a solution containing an unsaturated polyester, an organic solvent for the polyester and a catalyst for further polymerization and thermosetting of the polyester, the core sheet comprising 20-70% by weight of resin. Impregnated and the impregnated core sheet is dried to a volatile content of 1-5% by weight; and (c) if desired, a backsheet impregnated with a thermosetting melamine / formaldehyde reaction product is crimped. A laminated product for high pressure decoration obtained by the method, wherein crimping is performed for 20 to 90 minutes at 115.6 ° C to 176.7 ° C (240 ° F to 3 ° C).
56.25kg / cm ² ~ 98.43kg / cm ² (800psi ~ at a temperature of 50 ° F)
1400 psi), the resulting compression laminate exhibits improved flexibility as demonstrated by packaging tests at room temperature, i.e. the resulting laminate has a diameter of 7.62 to 12.7 cm.
(3 to 5 inches) can be wrapped, whereas a laminate having a core sheet impregnated with a melamine / formaldehyde reaction product can only be wrapped to a diameter of 12.7 to 15.2 cm (5 to 6 inches). .