WO2007134544A1

WO2007134544A1 - Resin composition, a method of preparing plastic-rubber article from it and its application

Info

Publication number: WO2007134544A1
Application number: PCT/CN2007/001664
Authority: WO
Inventors: Haibo Jiang
Original assignee: Starlight Plastic Material (Shenzhen) Limited
Priority date: 2006-05-22
Filing date: 2007-05-22
Publication date: 2007-11-29
Also published as: CN100560650C; CN1884365A

Abstract

A resin composition, a method of preparing plastic-rubber article from it and its application. The resin composition comprise 25-90wt% of a basic resin, 5-70wt% of a substance containing butadiene, and 0.1-5wt% thermostability-differential pigment(s). The basic resin is one or a mixture of two of more selected from polymethyl methacrylate, polyethyl methacrylate, or polybutyl methacrylate. The resin composition can be used for engraving words or patterns on plastic-rubber articles by laser radiation. The resultant engraved words or patterns can not be peeled off easily. The preparation and use of articles are friendly to environment and the articles can be produced in high efficiency and with low cost.

Description

Resin composition, method for producing the same, and application of the same

The present invention relates to a resin composition for preparing a plastic part of a card, a telephone, a computer keyboard, a facsimile machine, and the like, and a method of preparing a plastic part, which is suitable for laser engraving. Background technique

Plastic parts for products such as cards, telephones, computer keyboards, and fax machines are generally injection-molded with resin materials such as ABS and HIPS (high-impact polystyrene resin). However, when the plastic parts made of these raw materials of the prior art form characters or patterns on the surface, generally only the ink screen printing method can be used, and the traditionally unchanged imprinting method has complicated operation, the working efficiency is too low, the cost is too high, and the environmental pollution is caused. , the product is not environmentally friendly. Moreover, this conventional mime printing method cannot be operated on irregular platforms, especially when forming characters or patterns in concealed places such as slits or openings. In addition, the characters or patterns formed by the mimeographing method are not resistant to acids, alkalis, and oils, and have poor abrasion resistance and are easy to fall off. Because of the limitations of existing materials, molded plastic products cannot be laser-engraved to form continuous smooth text or patterns. Summary of the invention

The technical problem to be solved by the present invention is to provide a resin composition whose surface of a plastic product is easy to form a continuous smooth character or pattern and which is not easy to fall off, the method for producing the plastic product, and the resin composition. Applications.

The technical solution adopted by the present invention to solve the technical problems thereof is to provide a resin composition comprising the following mass percentage components:

Base resin 25~90% butadiene-containing substance 5-70%

Thermal stability difference pigment 0.1-5%

Wherein the base resin is a mixture of one or more selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, or polybutyl methacrylate.

The resin composition further includes an antioxidant having a mass percentage of 0.1 to 1%, respectively, and is thermally stable. And a foaming agent, the thermal stability difference pigment has a difference in thermal stability from the base resin, and there is a difference in thermal stability between the plurality of pigment components.

The resin composition is produced in the following manner:

(1) Grinding the base resin into a fine powder to facilitate thorough mixing with other ingredients;

(2) Put the powdery base resin into the kneader, add the butadiene-based substance and the thermal stability difference pigment, and knead and heat at 200~220 °C under vacuum and high pressure for 40~60 minutes until plastic Refined into a uniform soft body glue;

(3) The kneaded soft body rubber is masticated at 180 to 200 ° C by a two-roll mill, and the soft body rubber is pressed into a sheet shape.

The butadiene group-containing substance is a mixture of one or a combination of butadiene, methacrylic acid-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene.

The mass percentage of each component is - base resin 39~70%

Butadiene-containing material 29-60%

Thermal stability difference pigment 0.1~1.0% Antioxidant 0.1~0.3% Heat stabilizer 0.1~0.3% Foaming agent 0.1~0.3%.

Another technical solution adopted by the present invention to solve the technical problems thereof is as follows: The manufacturing method of the plastic product mainly includes the following steps:

(1) Use the following mass percentage components:

Basic resin 25~90%

Butadiene-containing material 5~70%

Thermal stability difference pigment 0.1-5%

Wherein the base resin is a mixture of one or more selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, or polybutyl methacrylate;

(2) Grinding the base resin into a fine powder to facilitate thorough mixing with other ingredients;

(3) Putting the powdery base resin into a kneader, adding a butadiene-containing substance and thermal stability Differential pigment, heated and kneaded under vacuum and high pressure until masticated into a uniform soft body glue;

(4) heating and kneading the kneaded soft body rubber by a two-roll mill to press the soft body rubber into a sheet shape;

(5) Forming the granular resin composition into a plastic product.

The method for manufacturing the plastic product further includes after step (5):

(6) The molded plastic product is engraved using a laser engraving machine to form a pattern or text.

The step (3) is carried out by heating under vacuum and high pressure at 200 to 220 ° C for kneading and kneading for 40 to 60 minutes until mastication into a uniform soft rubber; the step (4) double roll mill is at 180 to 200 ° Mastication is carried out under C; in the step (6), the power of the laser engraving machine is 50W, and the laser speed is 7Kmm/s.

The invention also provides for the use of the resin composition in laser engraving.

The resin composition is laser engraved to form a pattern or a character.

Advantageous Effects of Invention The plastic article molded by the resin composition of the present invention is suitable for laser engraving, and the surface of the product is liable to form a continuous smooth text or pattern and is not easily peeled off. The method of forming characters or patterns has a good environmental protection effect, the working efficiency can be increased by more than 30 times, the cost can be reduced by 10 times, the precision is high, and marks can be formed on the irregular plane, especially in the hidden places such as slits or openings. Security. In addition, the formed characters or patterns are more than 50 times more resistant to stencil printing, are less likely to fall off, and are resistant to acids, alkalis, oils, etc., and are suitable for use in different regions and complex environments.

The components of the resin composition of the present invention are extremely uniformly mixed in the particles, ensuring uninterrupted lines of the engraved characters or patterns. detailed description

The resin composition of the present invention mainly comprises the following mass percentage components:

Lane 3⁄4 >3⁄4 day 25-90%

Butadiene-containing material 5-70%

Thermal stability difference pigment 0. 5.0%

Antioxidant 0.1-1%

Heat stabilizer 0.1-1% Foaming agent 0.1~1%

The base resin is a mixture of one or more of polymethyl methacrylate (PMMA), polyethyl methacrylate, or polybutyl methacrylate. PMMA or the like may be in the form of powder or granules, which itself has a transparent gloss, is strong in rigidity, has good abrasion resistance, and has good foaming properties.

The butadiene-containing substance means a mixture of one or more of butadiene, MBS, ABS, and the like. MBS is a methacrylic acid-butadiene-styrene copolymer, ABS is acrylonitrile-butadiene-styrene, butadiene is a butadiene latex or an emulsion polymerization solution containing butadiene as a main monomer. Butadiene MBS, ABS and other rubber properties with good elasticity and impact strength can change the softness of PMMA to suit various moldings. More importantly, it can be combined with PMMA to make the resin composition semi-transparent magnetic white. , can be used as a base color.

Thermal stability The thermal stability of the pigment differs from the thermal stability of the resin composition, and there is a difference in thermal stability between the components of the composite pigment, which can be separated under transient heating conditions to produce different colors.

The role of the antioxidant is to inhibit the oxidative degradation of the polymer during the refining process, to prevent oxidation of the engraved part of the material during the laser engraving process, to avoid affecting the engraving effect, and the antioxidant is generally selected from a phenolic antioxidant or an amine antioxidant. . The function of the heat stabilizer is to prevent thermal decomposition and heat aging during polymer processing, and to avoid affecting the engraving effect. The heat stabilizer is generally selected from polyvinyl chloride or vinyl chloride copolymer. The blowing agent can be azodicarbonamide or other blowing agents of the prior art.

39-70%

29-60%

-1.0%

-0.3%

The processing method of the resin composition of the present invention mainly comprises the following steps:

(1) PMMA is ground into a fine powder to facilitate thorough mixing with other ingredients;

(2) Put the powdered PMMA into the kneading machine, add polybutadiene latex or mainly butadiene To the monomer emulsion polymerization solution, add pigment, antioxidant, heat stabilizer, foaming agent, etc., or add other additives as needed, knead and knead under vacuum, high pressure, 200~220 °C 40~ 60 minutes, until masticated into a soft rubber gel;

(3) Molding the kneaded soft body glue in a two-roll mill at 180 to 200 ° C, and pressing the soft body rubber into a sheet shape;

(4) cooling the sheet-like rubber block and pulverizing to form fine flaky particles;

(5) Use a pelletizer to mix the wire to cut the fine piece into a regular granular shape.

The pellets of the composition formed by the above steps (4) and (5) may be directly packaged for sale, or may be directly formed into a plastic product as a raw material, and further comprise the following steps when forming the plastic product:

(6) Forming an article by injection molding a granular resin composition or other molding method of the prior art, 'such as injection molding into a plastic part of a telephone, a mobile phone, a calculator, or the like;

(7) The formed product is engraved with a laser engraving machine to form a pattern or text, in which the power of the laser engraving machine can be selected as 50W, and the laser speed can be selected as 7Kmm/s.

The resin composition of the present invention contains the following components and properties:

(1) thermal stability difference pigments;

(2) PMMA itself has good foaming properties;

(3) Butadiene has a property of softening PMMA and combining it with PMMA to form a magnetic white color; therefore, the resin composition pellets produced by the above method have good foaming property, and exist between the pigment and the resin composition itself and the composite pigment. The difference in thermal stability. At the high temperature of the laser scanning, the portion to be fired is rapidly heated and foamed, and the component with poor thermal stability of the pigment is separated from the component with high thermal stability to produce a heterochromatic color, so that the formation is constant. The three-dimensional font or pattern.

The product formed by using the composition is suitable for laser engraving to form smooth and continuous lines or patterns of various lines, such as black products can engrave white writing or patterns, purple products can engrave blue or red text or patterns, green products It can be engraved with yellow text or patterns, and dark blue can be engraved with purple and red. Compared with the traditional stencil printing method, the method for forming characters or patterns has a good environmental protection effect, the working efficiency can be improved by more than 30 times, the cost can be reduced by 10 times, the precision is high, and the irregularity can be on the irregular plane, especially the slit or the opening. Marks such as holes form marks for anti-counterfeiting. In addition, the formed characters or patterns are 50 times or more anti-wearing properties, which are not easy to fall off, and have properties such as acid resistance, alkali resistance and oil resistance. Use in areas and complex environments.

The preparation method of the resin composition of the present invention is simple in process, and the composition of the formed particles is extremely uniform in mixing, ensuring uninterrupted lines of the engraved characters or patterns.

In this example, a resin composition of the present invention, a method for producing the same, and a method for producing the product will be described by taking a black product engraving to form a white character or a pattern. The resin composition is blended in the following mass percentages:

Powdered PMMA resin 75%

Butadiene latex 24.5%

Thermally stable black pigment 0.5% ·

The manufacturing method of the product includes the following steps:

(1) selecting the material into the kneading machine according to the above formula, kneading and kneading under vacuum, high pressure, 200~220 °C for 40 to 60 minutes, until masticating into a uniform soft body glue;

(2) The kneaded soft rubber is plasticized by a two-roll mill under heating conditions of 180 to 200 ° C to press the soft body rubber into a sheet shape;

(3) cooling the sheet-like rubber block and pulverizing to form fine flaky particles;

(4) using the particles of step (3) as raw materials to be injected into a telephone button;

(5) Put the telephone button into the laser engraving machine, laser engraving at a power of 50W and a laser speed of 7Kmm/s, thereby forming a white number on the telephone button and forming a white mark and pattern on the phone casing.

The principle of forming white numbers, signs and patterns is: At the high temperature of the laser scanning, the black telephone button material is made of the resin and the carbon black pigment, and the thermal stability of the carbon black pigment is higher than that of the resin. The composition, under the instantaneous high-temperature scanning condition of the laser, the resin is instantaneously dissolved and foamed by heat, so that the magnetic white of the resin itself is separated from the carbon black powder, and the white component of the scanning portion is convex to produce a white handwriting or pattern with a three-dimensional effect. In this example, the resin composition of the present invention is illustrated by exemplifying a yellow text or a pattern in a light green product. The preparation method thereof and the method of producing the product. The resin composition is proportioned by the following mass percentages:

Powdered PMMA resin 75%

Butadiene latex 24.5%

Green composite pigment 0.5%

The green composite pigment with different thermal stability is made of titanium blue and yellow pigment in a green color of 3:1. To make the product engrave yellow text or pattern, the thermal stability of the yellow pigment in the composite pigment and the resin itself The thermal stability is the same, and their thermal stability is lower than that of the titanium cyanine pigment.

The manufacturing method of the product includes the following steps:

(4) injection molding into a green plastic casing using the pellet of step (3) as a raw material;

(5) The green plastic case is placed in a laser engraving machine and laser-engraved at a power of 50W and a laser speed of 7Kmm/s to form a yellow text or pattern on the plastic casing.

The principle of forming a yellow text or pattern is that the portion irradiated by the laser is instantaneously heated and foamed by the high temperature, and the yellow pigment and the magnetic white resin have the same melting point, the phase dissolves to form yellow, and the foaming action and the thermal stability are strong. The blue phase separates to form a yellow text or pattern.

Claims

The present invention provides a temporary composition comprising the following mass percentage components: base resin 25-90% butadiene-containing material thermal stability difference pigment 0.1-5% wherein the base resin is selected from polymethyl methacrylate a mixture of one or more of polyethyl methacrylate, or polybutyl methacrylate. The resin composition according to claim 1, wherein the resin composition further comprises an antioxidant, a heat stabilizer and a foaming agent in a mass percentage of 0.1 to 1%, respectively, the thermal stability. The thermal stability of the difference pigments is different from that of the basic tree and the fat, and there are differences in the thermal stability between the various pigment components. The resin composition according to claim 1, wherein the resin composition is produced by the following method:

(2) Put the powdery base resin into the kneading machine, add the butadiene-based substance and the thermal stability difference pigment, and heat and knead at 200~220 °C under vacuum and high pressure for 40~60 minutes, until plastic Refined into a uniform soft body glue;

(3) The kneaded soft rubber is masticated at 180 to 200 ° C by a two-roll mill, and the soft rubber is pressed into a sheet.

The resin composition according to any one of claims 1 to 3, wherein the butadiene group-containing substance is selected from the group consisting of butadiene, methacrylic acid-butadiene-styrene copolymer, A mixture of one or more of acrylonitrile-butadiene-styrene.

The resin composition according to claim 4, wherein the mass percentage of each component is:

Basic resin 39-70%

Butadiene-containing material 29-60% Thermal stability difference pigment 0.1-1.0%

Antioxidant

Heat stabilizers

Foaming agent 0.1-0.3%

6. The manufacturing method of plastic products mainly includes the following steps:

(1) Use the following mass percentage components:

Base resin 25-90% butadiene-containing material

Thermal stability difference pigment

(3) Putting the powdery base resin into a kneader, adding a butadiene-based material and a thermal stability difference pigment, and heating and kneading under vacuum and high pressure until masticating into a uniform soft rubber;

(5) The granular resin composition is molded into a plastic product.

7. The method of manufacturing a plastic article according to claim 6, further comprising: after step (5) comprising:

The method for manufacturing a plastic article according to claim 7, wherein the step (3) is carried out by heating under vacuum and high pressure at 200 to 220 Torr for kneading for 40 to 60 minutes until mastication into a uniform software. The step (4) is a double-roll mill performing mastication at 180 to 200 Torr; in the step (6), the power of the laser engraving machine is 50 W, and the laser speed is 7 Kmm/s.

9. The method of manufacturing a plastic article according to claim 6, wherein: the resin composition further comprises an antioxidant, a heat stabilizer and a foaming agent in a mass percentage of 0.1 to 1%, respectively. The thermal stability difference pigment has a difference in thermal stability from the base resin, and there is a difference in thermal stability between the plurality of pigment components.

The method of producing a plastic article according to claim 6, wherein the butadiene group-containing substance is selected from the group consisting of butadiene, methacrylic acid-butadiene-styrene copolymer, and acrylonitrile-butyl. a mixture of one or more of diene-styrene.

The method of producing a plastic article according to any one of claims 6 to 10, wherein the mass percentage of each component is:

39-70%

29-60%

0. Bu 1.0%

0.1-0.3%

12. Use of the resin composition of claim 1 in laser engraving.

The use of the resin composition according to claim 12 for laser engraving, characterized in that the resin composition is laser-engraved to form a pattern or a character.

The use of the resin composition according to claim 12 for laser engraving, characterized in that the resin composition further comprises an antioxidant, a heat stabilizer and a foaming agent in a mass percentage of 0.1 to 1%, respectively. The thermal stability difference pigment has thermal stability different from that of the base resin, and there are differences in thermal stability between the plurality of pigment components.

The use of the resin composition according to claim 12 for laser engraving, characterized in that: the resin composition is produced by the following method:

(2) Put the powdery base resin into the kneading machine, add the butadiene-based material and the thermal stability difference pigment, and knead and heat at 200~220 °C under vacuum and high pressure for 40~60 minutes, until plastic Refined into a uniform soft body glue; (3) The kneaded soft body rubber is masticated at 180 to 200 ° C by a two-roll mill, and the soft body rubber is pressed into a sheet shape.

The use of the resin composition according to any one of claims 12 to 15 for laser engraving, characterized in that the butadiene group-containing substance is selected from the group consisting of butadiene and methacrylic acid-butadiene. a mixture of one or more of a styrene copolymer, acrylonitrile-butadiene-styrene.

The use of the resin composition according to claim 16 for laser engraving, characterized in that: the mass percentage of each component is:

Basic resin 39~70%

Butadiene-containing material 29~60%

Thermal stability difference pigment 0.1~1.0%

Antioxidant 0.1~0.3%

Heat stabilizer 0.1~0.3%

Foaming agent 0.1~0.3%.