JPH03106633A - Manufacture of propylene resin having hard coated layer - Google Patents

Abstract

PURPOSE:To manufacture a propylene resin article having hard coated layer by forming a film of acrylic ultraviolet ray curing resin on a specific propylene resin film or sheet surface and, after being subjected to a heat molding process, curing the ultraviolet ray curing resin by applying ultraviolet rays on the film. CONSTITUTION:Propylene resin used herein is of a type wherein a half amount of the total crystallization amount obtained from an isothermal crystallized curve at 140 deg.C by a differential scanning calorimeter requires 10<4> seconds or less in its crystallization time gamma1/2. It consists of acrylic resin and photopolymerization initiator acrylic polymerization monomer added as required. The formation of a film of acrylic ultraviolet ray curing resin is performed such that a solution in which the resin is solved in a solvent is applied on the surface of the propylene resin film of sheet which is given a pretreatment such as washing, etching, corona discharge or the like as required preliminarily in order that the thickness thereof after removing the solvent becomes preferably 3-30mu, after that the solvent is removed therefrom in heating. Next, it is subjected to a heat molding process and then ultraviolet rays are applied to the formed film so as to cure the ultraviolet ray curing resin.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a propylene-based resin dignified article having a high-gloss hard coat layer, and in particular, to a method for manufacturing a propylene-based resin-based article having a high-gloss hard coat layer, and in particular, to a method for producing an exterior of a car, home appliance, etc. using a propylene-based resin. It is useful in manufacturing parts, interior parts, etc.

[Conventional technology]

Propylene resin is widely used in various industrial parts such as automobiles and home appliances due to its light weight and ease of processing. Among these, scratch resistance is required for exterior and interior parts. In such applications, methods are employed to provide scratch resistance by forming, for example, a hard coat layer of acrylic ultraviolet curable resin on the surface of the propylene resin molded product. As a method for manufacturing a propylene-based resin prestige article having a hard coat layer, the present inventors formed a coating of acrylic ultraviolet curable resin on the surface of a propylene-based resin film or sheet, and then After being subjected to a desired shaping process such as shaping and/or thermoforming, the coating is irradiated with ultraviolet rays to cure the ultraviolet curable resin, thereby producing a propylene resin molded article having a hard coat layer. We developed this method and have already applied for a patent (Japanese Patent Application No. 4082/1982).

However, in the process of further developing the method for manufacturing brobylene-based resin shaped articles having the aforementioned hard coat layer, the present inventors discovered that the brobylene-based resin shaped articles subjected to the heat molding process: The problem faced was that the gloss of the hard coat layer formed was significantly poor. This problem does not exist in the conventional technology, which involves forming a film of ultraviolet curable resin on the surface of a molded product after hot molding, and then irradiating it with UV rays to form a hard coat layer. ,
This was a problem specific to the method of the aforementioned patent application.

[Problems to be Solved by the Invention] The present invention has been made to solve the aforementioned problems in the method for manufacturing a propylene resin molded product having a hard coat layer, for which the present inventors have previously applied for a patent. Therefore, an object of the present invention is to provide a method for producing a propylene-based resin shaped article having a high-gloss hard coat layer. [Means for Solving the Problems] The method for producing a propylene-based resin shaped article having a hard coat layer according to the present invention will be described in detail below. After forming a film and subjecting it to a thermoforming process, the film is irradiated with ultraviolet rays to cure the ultraviolet curable resin, thereby producing a propylene-based resin molded article having a hard coat layer. As for the resin, the time required for half of the total crystallization amount to crystallize, determined from the isothermal crystallization curve at 140°C using a differential scanning calorimeter, is τ1/
! is characterized in that the time is 104 seconds or less. Refers to single-layer and multi-layer films or sheets shaped by copolymers with α-olefins such as butene-1, and modified products of these with maleic anhydride.

In the present invention, for this propylene resin, half of the total crystallization amount determined from an isothermal crystallization curve at 140°C using a differential scanning calorimeter is determined as ? Time required for crystallization τ17. However, it is essential to use a time period of 104 seconds or less, preferably 5×103 seconds or less, particularly preferably 103 seconds or less. This is because if τ,78 exceeds 104 seconds, the hard coat layer formed on the surface of the brobylene resin molded product will have significantly poor gloss. Note that the τ17■ of the propylene resin itself generally exceeds 104 seconds, and in order to make the τ,/wealth of the propylene resin 104 seconds or less as in the present invention, specifically, for example, In the resin, aluminum ξnium benzoate, aluminum pt-butylbenzoate, basic aluminum ξnium dibenzoate, basic aluminum di(pt-butylbenzoate), sodium pt-butylbenzoate, etc. , metal salts of aromatic carboxylic acids such as benzoic acid, metal salts of aromatic phosphate esters such as sodium di(4-t-butylphenyl) phosphate, dibenzylidene sorbitol, ';-p-methylbenzylidene sorbitol, p-ethylbenzylidene sorbitol, p-isobrobylbenzylidene sorbitol, di-p-chlorobenzylidene sorbitol, p-methylbenzylidene-p-ethylbenzylidene rubitol, p-methylbenzylidene-p-isopropylbenzylidene sorbitol, p-
Methylbenzylidene-p-chlorobenzylidene sorbitol, p-ethylbenzylidene-p-isopropylbenzylidene sorbitol, p-ethylbenzylidene-p-
Chlorobenzylidene sorbitol, p-isopropylbenzylidene-p-chlorobenzylidene sorbitol, etc.
An example of this is to include about 0.01 to 1% by weight of a so-called nucleating agent, typified by a condensate of a polyhydric alcohol such as sorbitol and an aldehyde such as benzaldehyde.

In addition, acrylic ultraviolet curable resins are typically
It refers to a composition consisting of an acrylic resin, a photopolymerization initiator, and an acrylic polymerizable monomer added as necessary. Specifically, examples of the acrylic resin include methyl methacrylate, methacrylic acid, etc. Homopolymers of ethyl, butyl methacrylate, etc., or these together with (meth)acrylic acid [in this specification, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid], methyl acrylate, Ethyl acrylate, butyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Copolymers with glycidyl, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc., and modified products in which (meth)acryloyl groups are introduced into the side chains of these copolymers, For example, (meth)acrylic acid is added to a copolymer of methyl methacrylate and (meth)glycidyl acrylate, or glycidyl (meth)acrylate is added to a copolymer of methyl methacrylate and (meth)acrylic acid. Tolylene diisocyanate or isophorone diisocyanate and (meth)acrylic M2 are added to a copolymer of methyl methacrylate and 2-hydroxyethyl (meth)acrylate, which is a modified product in which epoxy (meth)acrylate is introduced by addition reaction.
Examples include modified products in which urethane (meth)acrylate is introduced by addition reaction of a reactant in an equimolar ratio with -hydroxyethyl. In addition, examples of photopolymerization initiators include:
Benzoin methyl ether, benzoin ethyl ether, penzoin isopropyl ether, penzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, l-hydroxycyclohexyl phenyl ketone,
Penzophenone, ξHiller's ketone, N,N-dimethylanobenzoic acid isoalξ, 2-chlorothioxanthone, 2,4-diethylthioxanthone, etc., and the acrylic polymerizable monomers include, for example, 2-methoxyethyl acrylate, 2-Ethoxyethyl acrylate, 2-phenoxyethyl acrylate, ethoxydiethylene glycol acrylate, phenoxydiethylene glycol acrylate, nonylphenol ethylene oxide adduct acrylate, nonylphenol propylene oxide adduct acrylate, penzyl acrylate, cyclohexyl acrylate, tetrahydrofuryl acrylate 1 Monofunctional acrylates such as Relylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 2-hydroxy-3-phenoxybrobyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyprobyl acrylate, 1,4-butanediol diacrylate , neopentyl glycol diacrylate, l,6-hexanediol diacrylate}, 2.2
-bis[4-(acryloyloxydiethoxy)phenyl]propane, bis(acryloyloxyethyl) hydroxyethyl isocyanurate, tricyclodecane dimethyl diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate,
Trimethylolpropane propylene oxide adduct triacrylate, tris(acryloyloxyethyl)
Examples include polyfunctional acrylates such as isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol repentaacrylate, and rylate.

The form of the coating of the acrylic UV curable resin, or the acrylic UV curable resin, for example, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as chloroform, ethylene dichloride, etc. methyl acetate,
Dissolve in ester-based solvents such as ethyl acetate and butyl acetate, ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ether-based solvents such as dioxane and cellosolve. After coating the surface of the thermoplastic resin film or sheet that has been pretreated with discharge etc. by a method such as roll coating or goo coating so that the thickness after removing the solvent is 1 to 50 μm, preferably 3 to 30 μm, This is done by heating to remove the solvent. Next, after being subjected to a thermoforming process, the formed film is irradiated with ultraviolet rays to cure the ultraviolet curable resin.

Here, the heat molding process refers to a brobylene resin film or sheet with an uncured coating formed on the surface, heated and melt-kneaded with an extruder on the back side as necessary, and then passed through a T-die into a single layer or sheet. Extrusion laminate or coextrusion laminate by pressing other thermoplastic resins extruded into multilayer sheets between rolls, or bonding preformed sheets of other thermoplastic resins with adhesive. After installing a dryer, etc., the desired mold is attached to a vacuum forming machine, a pressurized air forming machine, a vacuum forming machine, a hot plate pressurizing forming machine, a stamping forming machine, etc. This refers to the process of shaping using a machine.

Examples of the ultraviolet irradiation device include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a tungsten lamp, and a halogen lamp.

[Action and effect]

The present invention involves forming an acrylic type ultraviolet curable resin coating on the surface of a propylene resin film or sheet, subjecting it to a thermoforming process, and applying ultraviolet rays to the coating. In manufacturing a propylene resin molded product having a hard coat layer by curing the ultraviolet curable resin by irradiating it with This problem can be solved by using a propylene-based resin that has the following properties.

〔Example〕

Example 1 By adding 0.1% by weight of dibenzylidene sorbitol to a propylene homopolymer, τI/t was increased to 5.8X.
After subjecting the surface of a propylene homopolymer film (thickness 100μ) to corona discharge treatment for 10 seconds, 100 parts by weight of methyl methacrylate homopolymer, 4 parts by weight of benzyl dimethyl ketal, and dipentaerythritol were added to the treated surface. A solution of 40 parts by weight of hexaacrylate, 10 parts by weight of neopentyl glycogol diacrylate, and 200 parts by weight of toluene was applied with a roll coater and heated to form a film on the melted surface.On the back side of the brobylene homopolymer film, propylene alone was applied. 30% by weight of polymer, 45% by weight of ethylene homopolymer (density 0.950 g/cm),
A resin composition containing 25% by weight of talc (average particle size 5 μm) was melt-extruded into a sheet and pressed between rolls to form an extrusion laminate (thickness: 2.8 m). Next, the obtained laminated sheet was heated to a surface temperature of 170°C, and shaped with a vacuum molding machine equipped with a mold (width 200mm, depth 150n, height 80mm) at an area magnification of 2.87 times. The resulting molded product is irradiated with ultraviolet light using a high-pressure mercury lamp with an output of 2 kN and an output density of 80 W/cm at a conveyor speed of 0.8 m/min to cure the ultraviolet curable resin, thereby creating a hard coat layer on the outer surface. A propylene resin prismatic container-shaped product was manufactured.

The obtained hard coat layer had a pencil hardness of 2H and a surface gloss of 72%.

Example 2 D-p-methylbenzylitensorhitol was added to propylene homopolymer in an amount of 0. Containing 1% by weight τ1
A propylene resin prismatic container-shaped article having a hard coat layer on the outer surface was produced in the same manner as in Example 1 except that a propylene homopolymer having /2 of 1.5XlO' seconds was used.

The obtained hard coat layer had a pencil hardness of 2H and a surface gloss of 76%.

Example 3 Adding 0.15% by weight of di-p-methylbenzylidene sorbitol to a propylene homopolymer.
A propylene-based resin prismatic container-shaped article having a hard coat layer on the outer surface was produced in the same manner as in Example 1 except that a propylene homopolymer having /1 of 3.3 x lO'' seconds was used.

The obtained hard coat layer had a pencil hardness of 2H and a surface gloss of 80%.

Example 4 τl/
A propylene-based resin prismatic container-shaped molded product having a hard coat layer on the outer surface was produced in the same manner as in Example 1 except that a propylene homopolymer having l of 1.7×10” seconds was used. The coating layer had a pencil hardness of 2H and a surface gloss of 86%. Example 5 By adding 0.15% of hydroxydi(1-butylbenzoate) aluminum to a propylene homopolymer, τ1/2 was reduced. 2. A brobylene-based resin rectangular container-shaped article having a hard coat layer on the outer surface was produced in the same manner as in Example 1, except that a propylene homopolymer having an IX10'' second was used.

The obtained hard coat layer had a pencil hardness of 2H and a surface gloss of 81%. Example 6 0.0% of aluminum hydroxydi(1-butylbenzoate) was added to a propylene homopolymer. By containing 3% by weight, τ. A propylene-based resin prismatic container or shaped article having a hard coat layer on the outer surface was manufactured in the same manner as in Example 1 except that a propylene homopolymer having a weight of 1.2 x lG'' seconds was used. The hard coat layer had a pencil hardness of 2H and a surface gloss of 84%. Example 7 As an ultraviolet curable resin, 15 parts by weight of dipentaerythritol hexaacrylate and 2 parts by weight of piperazine were mixed in 83 parts by weight of methyl ethyl ketone. Propylene having a hard coat layer on the outer surface was prepared in the same manner as in Example 1, except that 0.5 parts by weight of benzyldimethylkecoel was dissolved in the reaction solution obtained by Michael addition reaction at 40°C for 3 hours. A rectangular container-shaped article of the resin was manufactured. The hard coat layer obtained had a pencil hardness of 3H and a surface gloss of 82%.

Comparative Example 1 A propylene-based resin rectangular container-shaped article having a hard coat layer on the outer surface was produced in the same manner as in Example 1, except that a propylene homopolymer with τ1/t of 2.6×104 seconds was used. The obtained hard coat layer had a pencil hardness of 2H and a surface gloss of 30%.

Claims (1)

[Claims] A hard coat layer is formed by forming a coating of acrylic ultraviolet curable resin on the surface of a propylene resin film or sheet, subjecting it to a thermoforming process, and then irradiating the coating with ultraviolet rays to harden the ultraviolet curable resin. In manufacturing a propylene-based resin molded article having the above-mentioned propylene-based resin, the time required for half of the total crystallization amount to crystallize τ_1_/ determined from an isothermal crystallization curve at 140°C using a differential scanning calorimeter. A method for producing a propylene-based resin molded product having a hard coat layer, characterized in that _2 is 10^4 seconds or less.