CN116463097A - Halogen-free adhesive for in-mold decoration and preparation method thereof - Google Patents
Halogen-free adhesive for in-mold decoration and preparation method thereof Download PDFInfo
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- CN116463097A CN116463097A CN202310542950.6A CN202310542950A CN116463097A CN 116463097 A CN116463097 A CN 116463097A CN 202310542950 A CN202310542950 A CN 202310542950A CN 116463097 A CN116463097 A CN 116463097A
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- free adhesive
- adhesive
- mold decoration
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- 239000000853 adhesive Substances 0.000 title claims abstract description 60
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 60
- 238000005034 decoration Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004417 polycarbonate Substances 0.000 claims abstract description 34
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229920001225 polyester resin Polymers 0.000 claims abstract description 15
- 239000004645 polyester resin Substances 0.000 claims abstract description 15
- 238000001746 injection moulding Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 21
- 238000007639 printing Methods 0.000 claims description 17
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 12
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021485 fumed silica Inorganic materials 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 229920005668 polycarbonate resin Polymers 0.000 claims description 4
- 239000004431 polycarbonate resin Substances 0.000 claims description 4
- 239000011265 semifinished product Substances 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 2
- 229910052794 bromium Inorganic materials 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- -1 isoparaffin Chemical compound 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 33
- 239000000976 ink Substances 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000012778 molding material Substances 0.000 description 5
- 229920006942 ABS/PC Polymers 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 2
- 235000010261 calcium sulphite Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a halogen-free adhesive for in-mold decoration and a preparation method thereof. It is composed of the following proportions: 25-55 parts of soluble modified polycarbonate, 0-15 parts of polyester resin, 1-10 parts of filler, 0.5-5 parts of non-silicon surface auxiliary agent and 30-69 parts of organic solvent. The preparation method comprises the following steps: the polycarbonate and the polyester resin are dissolved in an organic solvent, after the filler is added into the resin liquid, the mixture is stirred on a stirrer for 10 minutes, the materials are ground on a three-roller machine for 2 times, then the surface auxiliary agent is added, and the mixture is stirred for 10 minutes, thus obtaining the halogen-free adhesive for the in-mold decoration process. The halogen-free adhesive is applied to an in-mold decoration process of an automobile interior trim part, a diaphragm printed with a preset pattern can be attached to an injection molding workpiece, so that the artistic design of the workpiece is realized, and meanwhile, the signal tolerance test requirement of the automobile interior trim part can be met.
Description
Technical Field
The invention relates to a halogen-free adhesive capable of being constructed through screen printing, in particular to a halogen-free adhesive for in-mold decoration and a preparation method thereof.
Background
After the In-mold Decoration (IMD) process realizes industrial production from Japan, the In-mold Decoration has diversified decorative designs, low cost and no-spraying environmental protection property, so that the In-mold Decoration has vigorous development of application In the industries of household appliances, mobile phones and automobiles; the special 3D pattern design is not replaced by the traditional spraying process.
In recent years, consumer awareness of environmental protection and safety of electronic products, especially high-end application scenes such as high-grade household appliances, mobile phones and automotive interiors, has been clearly specified by a plurality of environmental regulations that inks and adhesives for IMD cannot contain excessive halogen, and most of adhesives for IMD technology currently sold on the market are halogen-containing vinyl chloride-vinyl acetate copolymer systems.
Accordingly, the prior art is still further developed and improved.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, it is an object of the present invention to provide a halogen-free adhesive for in-mold decoration, which can meet the environmental requirements of high-end products.
To achieve the purpose, the invention adopts the following technical scheme:
a halogen-free adhesive for in-mold decoration, comprising:
wherein the content of the modified polycarbonate may be 25 parts, 30 parts, 38 parts, 42 parts, 55 parts, etc., the content of the polyester resin may be 0 part, 3 parts, 5 parts, 8 parts, 10 parts, 15 parts, etc., the filler may be one or more of fumed silica, bentonite, barium sulfate, calcium carbonate, the total content of the filler may be 1 part, 3 parts, 5 parts, 8 parts, 10 parts, etc., the non-silicon surface auxiliary agent may be an acrylic defoamer and an acrylic leveling agent, the total amount thereof may be 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc., the organic solvent may be one or more of isoparaffin, cyclohexanone, trimethylbenzene, tetramethylbenzene, dibasic ester, etc., and the total amount thereof may be 42 parts, 50 parts, 55 parts, 65 parts, 69 parts, etc. The formulations according to the present invention are not limited to the listed values, and other non-listed values within each of the above ranges are equally applicable.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
As a preferred technical scheme, the adhesive comprises the following components in 100 parts by weight:
the modified polycarbonate is used as a main material of the adhesive, has higher cohesive strength and mainly plays a role in adhesion; the polyester resin is used for adjusting the flexibility of the adhesive and is beneficial to the interlayer adhesive force between the adhesive and the matched printing ink; fumed silica and bentonite serve as rheological aids, and play a role in improving printing workability in the adhesive; barium sulfate and calcium carbonate are used as filling materials, and play a role in reinforcing the dry film of the adhesive in the adhesive; the mixed solvent of the tetramethylbenzene, the trimethylbenzene, the dibasic ester, the isoparaffin and the cyclohexanone is used for adjusting the production construction viscosity and the use construction viscosity of the adhesive; the non-silicon defoamer and the leveling agent play a role in improving the printing workability and the printing appearance in the adhesive.
Another object of the present invention is to provide a method for preparing a halogen-free IMD adhesive, the method comprising the steps of:
dissolving polyester resin in an organic solvent under stirring to obtain polyester resin liquid;
adding the modified polycarbonate resin liquid into the polyester resin liquid under the stirring condition to obtain a premix;
adding filler into the premix under stirring, and grinding on grinding equipment to obtain a semi-finished product;
and adding a non-silicon surface auxiliary agent into the semi-finished product under the stirring condition, and supplementing loss and adjusting viscosity by using an organic solvent to obtain the halogen-free adhesive for in-mold decoration.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The invention provides a halogen-free adhesive for in-mold decoration, wherein the total halogen content of the adhesive is lower than 900ppm, which accords with international and domestic environmental protection regulations and is different from the traditional halogen-containing adhesive for in-mold decoration;
(2) The invention provides a halogen-free adhesive for in-mold decoration, which has high strength and shearing strength of up to 7MPa;
(3) The invention provides a halogen-free adhesive for in-mold decoration, which has excellent adhesion to ABS, ABS/PC alloy plastic, PC and PC/GF;
(4) The invention provides a halogen-free adhesive for in-mold decoration, which has good high temperature resistance and weather resistance.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The halogen-free adhesive for in-mold decoration comprises the following components in 100 parts by weight:
the preparation method of the halogen-free adhesive for in-mold decoration comprises the following steps:
(1) Taking 95 parts of modified polycarbonate resin liquid, wherein the resin liquid contains 38 parts of modified polycarbonate solid parts and 57 parts of isoparaffin, the molecular weight of the modified polycarbonate is 20000, and the glass transition temperature is 157 ℃;
(2) 2 parts of bentonite APA of the German Pick company are added into the step (1) under the stirring of 600 revolutions per minute, and the mixture is stirred for 10 minutes;
(3) Grinding the materials on a three-roller machine for 1 time, wherein the fineness is less than 5um;
(4) Adding 1.5 parts of defoaming agent BYK-053N and 1.5 parts of flatting agent BYK-358N of Pick Germany into the material in the step (3) under the stirring of 600 revolutions per minute, stirring for 10 minutes, and packaging after the test is qualified.
Example 2
The halogen-free adhesive for in-mold decoration comprises the following components in 100 parts by weight:
the preparation method of the halogen-free adhesive for in-mold decoration comprises the following steps:
(1) 95 parts of modified polycarbonate is taken, wherein the modified polycarbonate contains 38 parts of modified polycarbonate solid, 30 parts of isoparaffin and 27 parts of tetramethylbenzene, the molecular weight of the modified polycarbonate is 32000, and the glass transition temperature is 182 ℃;
(2) 1 part of bentonite APA from Pick Germany and 1 part of fumed silica M-5 from cabot are added to the step (1) under stirring at 600 revolutions per minute, and stirring is carried out for 10 minutes;
(3) Grinding the materials on a three-roller machine for 1 time, wherein the fineness is less than 5um;
(4) Adding 1.5 parts of defoaming agent BYK-053N and 1.5 parts of flatting agent BYK-358N of Pick Germany into the material in the step (3) under the stirring of 600 revolutions per minute, stirring for 10 minutes, and packaging after the test is qualified.
Example 3
The halogen-free adhesive for in-mold decoration comprises the following components in 100 parts by weight:
the preparation method of the halogen-free adhesive for in-mold decoration comprises the following steps:
(1) Taking 90 parts of modified polycarbonate, wherein the modified polycarbonate comprises 35 parts of modified polycarbonate solid, 35 parts of isoparaffin, 10 parts of tetramethylbenzene, 5 parts of trimethylbenzene and 5 parts of dibasic ester, the molecular weight of the modified polycarbonate is 39000, and the glass transition temperature is 185 ℃;
(2) 1 part of bentonite APA of the German Pick company, 1 part of fumed silica M-5 of the Kabot company, 3 parts of barium sulfate HU-N of the Harli company of Finnish, 2 parts of calcium carbonate Omyacarb 2-JI of the Europe-England European calcium sulfite company of the Hemsleyaite company are added to the step (1) under the stirring of 600 revolutions per minute, and the mixture is stirred for 10 minutes;
(3) Grinding the materials on a three-roller machine for 2 times, wherein the fineness is less than 5um;
(4) 1.5 parts of defoaming agent AC368 of Japanese co-Rong company and 1.5 parts of leveling agent NO.77 are added to the material in the step (3) under the stirring of 600 revolutions per minute, the stirring is carried out for 10 minutes, and the packaging is carried out after the inspection is qualified.
Example 4
The halogen-free adhesive for in-mold decoration comprises the following components in 100 parts by weight:
the preparation method of the halogen-free adhesive for in-mold decoration comprises the following steps:
(1) Taking 5 parts of Toyo-spun Vylon 885, and dissolving in 10 parts of cyclohexanone;
(2) 75 parts of modified polycarbonate is taken and added to the polyester resin liquid in the step (1). The liquid-phase synthesized modified polycarbonate resin liquid contains 30 parts of modified polycarbonate solid parts, 25 parts of isoparaffin, 10 parts of tetramethylbenzene, 5 parts of trimethylbenzene and 5 parts of dibasic ester, wherein the molecular weight of the modified polycarbonate is 32000, and the glass transition temperature is 182 ℃;
(2) 1 part of bentonite APA of the German Pick company, 1 part of fumed silica M-5 of the Kabot company, 3 parts of barium sulfate HU-N of the Harli company of Finnish, 2 parts of calcium carbonate Omyacarb 2-JI of the Europe-England European calcium sulfite company of the Hemsleyaite company are added to the step (1) under the stirring of 600 revolutions per minute, and the mixture is stirred for 10 minutes;
(3) Grinding the materials on a three-roller machine for 2 times, wherein the fineness is less than 5um;
(4) 1.5 parts of defoaming agent AC368 of Japanese co-Rong company and 1.5 parts of leveling agent NO.77 are added to the material in the step (3) under the stirring of 600 revolutions per minute, the stirring is carried out for 10 minutes, and the packaging is carried out after the inspection is qualified.
The evaluation test method for the above samples is as follows:
(1) Printability: and (3) at normal temperature and pressure, rapidly and continuously printing the adhesive with proper viscosity by using a semi-automatic printer, wherein the substrate is PET or PC film, and observing whether the ink surface is flat or not, and the printing defects such as orange peel, poor defoaming and the like are caused.
(2) Adhesion force: printing adhesive on a pattern printing surface of two-liquid hardening type ink such as PC sheet or PET film easy to be adhered and treated, then thoroughly drying (80-100 ℃ C. Multiplied by 60-90 min), then carrying out injection molding by using different injection molding materials, after cooling, scribing 1x1mm hundred lattice on the film surface, testing the adhesion force between the ink and PET substrate by using a blade or pliers (the edge of a 5B-notch is smooth, the edge of a lattice is not peeled off any more, the intersection of the 4B-notch is provided with small pieces, the actual breakage in the scribing area is not more than 5%, the edge and/or intersection of the 3B-notch is peeled off, the area is more than 5% but not more than 15%, 2B-is peeled off or peeled off in whole along the edge of the notch, and/or the lattice is peeled off in whole by 15% but not more than 35%, 1B-is peeled off in part or peeled off in whole by more than 35%, and/or the lattice is peeled off in whole by more than 65%, and/or the lattice is peeled off in part by more than 65% along the edge of the notch;
(3) Halogen: reference EN14582:2016, halogen content by ion chromatography;
(4) Shear strength: printing a sample on a PC sheet with the thickness of 1mm through 350 meshes, fixing two sample sheets on a coating surface by using DP420 epoxy glue of 3M company, controlling the thickness of the glue to be 0.125mm through a tool, baking at 80 ℃ for 60 minutes for curing, testing shearing force through a universal material testing machine, calculating the area of the glue through a CCD, and further calculating the shearing strength of the coating;
(5) Temperature resistance: printing an adhesive on a pattern printing surface of a PC sheet or a two-liquid hardening type ink which is easy to bond and process a PET film and the like through silk screen printing, thoroughly drying (80 ℃ multiplied by 90 minutes), then carrying out injection molding by using different injection molding materials, and baking an injection molding part at 105 ℃ for 240 hours, wherein the adhesive layer cannot be peeled from the IMD ink and the injection molding materials;
(6) Weather resistance: the adhesive is silk-screened on the pattern printing surface of two-liquid hardening type printing ink such as PC sheet or PET film easy to be adhered, and then thoroughly dried (80 ℃ multiplied by 90 minutes), then different injection molding materials are used for injection molding, the injection molding piece is placed in a constant temperature and humidity box with the temperature of 85 ℃ and the humidity of 85 parts, and the glue layer, the IMD printing ink and the injection molding material cannot be peeled off after standing for 240 hours.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Printability | In general | Good quality | Excellent and excellent properties | Excellent and excellent properties |
| Shear Strength/MPa | 6.5 | 6.7 | 9.5 | 9.2 |
| ABS adhesion | 3B | 4B | 4B | 4B |
| ABS/PC adhesion | 4B | 4B | 4B | 4B |
| PC adhesion force | 4B | 4B | 4B | 4B |
| PC/GF adhesion | 4B | 4B | 4B | 4B |
| ABS temperature resistance | Qualified product | Qualified product | Qualified product | Qualified product |
| ABS/PC temperature resistance | Qualified product | Qualified product | Qualified product | Qualified product |
| PC temperature resistance | Qualified product | Qualified product | Qualified product | Qualified product |
| PC/GF temperature resistance | Qualified product | Qualified product | Qualified product | Qualified product |
| ABS weatherability | Qualified product | Qualified product | Qualified product | Qualified product |
| ABS/PC weather resistance | Qualified product | Qualified product | Qualified product | Qualified product |
| PC weather resistance | Qualified product | Qualified product | Qualified product | Qualified product |
| PC/GF weather resistance | Qualified product | Qualified product | Qualified product | Qualified product |
In summary, the invention provides a halogen-free adhesive for in-mold decoration and a preparation method thereof, wherein the adhesive comprises the following main components in percentage by weight: 25-55 parts of soluble modified polycarbonate, 0-15 parts of polyester resin, 1-10 parts of filler, 0.5-5 parts of non-silicon surface auxiliary agent and 30-69 parts of organic solvent. The preparation method comprises the following steps: the polycarbonate and the polyester resin are dissolved in an organic solvent, after the filler is added into the resin liquid, the mixture is stirred on a stirrer for 10 minutes, the materials are ground on a three-roller machine for 2 times, then the surface auxiliary agent is added, and the mixture is stirred for 10 minutes, thus obtaining the halogen-free adhesive for the in-mold decoration process. The halogen-free adhesive is applied to an in-mold decoration process of an automobile interior trim part, a diaphragm printed with a preset pattern can be attached to an injection molding workpiece, so that the artistic design of the workpiece is realized, and meanwhile, the signal tolerance test requirement of the automobile interior trim part can be met.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. A halogen-free adhesive for in-mold decoration, characterized by comprising the following components in proportion: 25-55 parts of soluble modified polycarbonate, 0-15 parts of polyester resin, 1-10 parts of filler, 0.5-5 parts of non-silicon surface auxiliary agent and 30-69 parts of organic solvent.
2. The halogen-free adhesive of claim 1, wherein the modified polycarbonate has a molecular weight of 10000-100000 and a glass transition temperature of 120-200 ℃; the molecular weight of the polyester resin is 3000-20000, and the glass transition temperature is 60-90 ℃; the hydroxyl value is 1-5mgKOH/g.
3. The halogen-free adhesive of claim 1 wherein the filler is selected from one or more of fumed silica, bentonite, calcium carbonate and barium sulfate.
4. The halogen-free adhesive of claim 1 wherein the non-silicon based surface aid is an acrylate defoamer and a leveling agent.
5. The halogen-free adhesive of claim 1 wherein the organic solvent is one or more of benzene, esters, and ketones.
6. The halogen-free adhesive of claim 5, wherein the organic solvent is selected from one or more of dibasic esters greater than 95% pure, trimethylbenzene, tetramethylbenzene, isoparaffin, and cyclohexanone.
7. The halogen-free adhesive of claim 1, wherein the halogen-free adhesive is less than 500ppm chlorine, less than 500ppm bromine, and less than 900ppm total chlorine and bromine.
8. The halogen-free adhesive of any of claims 1-7, wherein the halogen-free adhesive is a one-component adhesive.
9. A method of preparing the halogen-free adhesive of any one of claims 1-8 comprising:
dissolving polyester resin in an organic solvent under stirring to obtain polyester resin liquid;
adding the modified polycarbonate resin liquid into the polyester resin liquid under the stirring condition to obtain a premix;
adding filler into the premix under stirring, and grinding on grinding equipment to obtain a semi-finished product;
and adding a non-silicon surface auxiliary agent into the semi-finished product under the stirring condition, and supplementing loss and adjusting viscosity by using an organic solvent to obtain the halogen-free adhesive for in-mold decoration.
10. A method of using the halogen-free adhesive of any one of claims 1-8, comprising the steps of:
printing IMD ink on a printing material, and baking for 10-30 minutes at 80-100 ℃ to obtain an IMD ink layer;
printing one or two layers of halogen-free adhesive on the IMD ink layer, and baking at 80-100 ℃ for 60-90 minutes;
solidifying and cooling, and then stamping, die cutting and injection molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310542950.6A CN116463097A (en) | 2023-05-15 | 2023-05-15 | Halogen-free adhesive for in-mold decoration and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310542950.6A CN116463097A (en) | 2023-05-15 | 2023-05-15 | Halogen-free adhesive for in-mold decoration and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116463097A true CN116463097A (en) | 2023-07-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310542950.6A Pending CN116463097A (en) | 2023-05-15 | 2023-05-15 | Halogen-free adhesive for in-mold decoration and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116463097A (en) |
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2023
- 2023-05-15 CN CN202310542950.6A patent/CN116463097A/en active Pending
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