CN105073921B - Aqueous surface-treating agent and the article for having used the aqueous surface-treating agent - Google Patents
Aqueous surface-treating agent and the article for having used the aqueous surface-treating agent Download PDFInfo
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- CN105073921B CN105073921B CN201480017380.8A CN201480017380A CN105073921B CN 105073921 B CN105073921 B CN 105073921B CN 201480017380 A CN201480017380 A CN 201480017380A CN 105073921 B CN105073921 B CN 105073921B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
Abstract
The present invention provides a kind of aqueous surface-treating agent and has used the article of the aqueous surface-treating agent, the aqueous surface-treating agent can make the surface of various articles turn into matt state and can assign the appearance design of more feeling of high class, also, it can be obtained by 1 coating even if being applied in the film that does not also reduce of delustring sense after the forming such as stretching.Use following aqueous surface-treating agents, it is characterised in that contain：Water-based polyurethane (A), waterborne polyester (B) or aqueous acrylic resin (C), delustering agent (D) and crosslinking agent (E).The use of above-mentioned waterborne polyester (B) is especially the aqueous surface-treating agent that polycarbonate-based aqueous polyurethane and above-mentioned crosslinking agent (E) are carbodiimide.
Description
Technical field
The present invention relates to a kind of aqueous surface-treating agent and the article of the aqueous surface-treating agent, the water-based table are used
Face inorganic agent can make the surface of various articles turn into matt (gloss disappearances) state and can assign more feeling of high class outside
See design.
Background technology
For various articles, in order to improve appearance design, assign feeling of high class, more in its external coating coating.Example
Such as, in order to pass through the housing to electronic equipments such as the housing of family's electrical article, computer, portable phone, smart mobile phones, automobile interior exterior fill
The surface of the formed products such as exterior material carries out delustring processing and assigns the appearance design with feeling of high class, usually using surface
Inorganic agent.It was mostly solvent system surface conditioning agent in the past as the surface conditioning agent, but due to producing VOC
(hereinafter referred to as " VOC ".) and environmental pressure is big, therefore seeking the reduction of VOC discharge rates, promote the water of surface conditioning agent
Property.
As making the surface of various articles turn into the aqueous surface-treating agent of matt state, such as following water is proposed
Property frosting inorganic agent, it contains：The aqueous urethane system of the polyol component comprising polyolefin polyhydric alcohol is used
Resin and as delustering agent polyurethane particulate (for example, with reference to patent document 1.).However, the water-based frosting inorganic agent
For the main aqueous surface-treating agent that delustring sense is realized using delustering agent, there is the problem of following in it：Such as on film or piece
After forming film, when stretch etc. forming, delustring sense reduces, gloss increase.
As the method that delustring sense does not reduce when carrying out the forming such as stretching, it is proposed that apply 2 containing delustering agent again
The method of kind smears is (for example, with reference to patent document 2.).However, this method needs multiple working procedure of coating and drying process, from
And there is problem in productivity ratio.
Therefore, seeking also not reduce and can be by 1 coating even if stretch etc. delustring sense after forming
Various articles are assigned with the aqueous surface-treating agent of sufficient delustring sense.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-342549 publications
Patent document 2：Japanese Unexamined Patent Publication 2006-176615 publications
The content of the invention
The invention problem to be solved
The problem to be solved by the present invention is that, there is provided a kind of aqueous surface-treating agent and use the aqueous surface-treating agent
Article, the aqueous surface-treating agent can turn into the surface of various articles matt state and can assign more high
The appearance design of level sense, also, can not obtained by 1 coating even if delustring sense after being applied in the forming such as stretching also not
The film of reduction.
The method for solving problem
The present inventor etc. have made intensive studies to solve above-mentioned problem, as a result find, for and used water-based poly-
For urethane and waterborne polyester or the aqueous surface-treating agent of aqueous acrylic resin as other resins, it can make each
The surface of kind article turns into matt state and can assign the appearance design of more feeling of high class, also, can pass through 1 painting
Apply and obtain, even if the film that delustring sense does not also reduce after stretching etc. forms is applied in, so far completing the present invention.
That is, the article of the aqueous surface-treating agent, the water have been used the present invention relates to a kind of aqueous surface-treating agent and
Property surface conditioning agent be characterised by containing：Aqueous polyurethane (A)；Waterborne polyester (B) or aqueous acrylic resin (C)；Disappear
Photo etching (D)；With crosslinking agent (E).
Invention effect
The aqueous surface-treating agent of the present invention can make the surface of various articles turn into matt state and can assign more
Has the appearance design of feeling of high class, even if also, can obtain being applied in delustring sense after the forming such as stretching by 1 coating
Also the film not reduced, thus, it can be used as the inorganic agent handled the surface of various articles.It can especially be suitable for moulding
Expect formed products, also, in formed products, can be particularly suited for belonging to thermoplastic olefin (Thermo Plastic
Olefin；Hereinafter referred to as " TPO ".) formed products, TPO leathers or TPO pieces.
Embodiment
The aqueous surface-treating agent of the present invention contains：Aqueous polyurethane (A)；Waterborne polyester (B) or water-borne acrylic type tree
Fat (C)；Delustering agent (D)；With crosslinking agent (E).
Above-mentioned aqueous polyurethane (A) as long as be dissolved or dispersed in the polyurethane of aqueous medium, wherein, preferably have
There is the polyurethane of carboxyl and/or hydroxyl.As the manufacture method of the polyurethane in the aqueous polyurethane (A) with hydroxyl, such as
It can enumerate：Make excessive polyalcohol and/or dihydric alcohol and polyisocyanates reaction and obtaining end has the polyurethane of hydroxyl
Method；Make the carbamate prepolymer and 2- ethylaminoethanols, 2- amino ethyl ethanolamines, diethanol amine of NCO end
Method of polyurethane with hydroxyl etc. is reacted and obtained Deng amino alcohol, amino phenols etc..On the other hand, as poly- with carboxyl
The manufacture method of urethane, such as can enumerate：Make using the compound with carboxyl as raw material and when urethane reacts
Method.
On the raw material as above-mentioned aqueous polyurethane (A) come the polyalcohol that uses, such as can enumerate：PEPA,
PPG, polycarbonate polyol, Polyacetal polyols, polyacrylate polyol, polyester amide polyol, polythiaether
Polyolefin polyhydric alcohols such as polyalcohol, polybutadiene system etc..Wherein, preferred polycarbonate polyol, because its durability is excellent
It is different.In addition, on the raw material as the polyurethane with carboxyl come the compound with carboxyl that uses, such as can enumerate：2,
2 '-dihydromethyl propionic acid, 2,2 '-dihydroxymethyl butane acid, 2,2 '-dihydroxymethyl butyric acid, 2,2 '-dihydroxymethyl valeric acid etc..Its
In, preferably 2,2 '-dihydromethyl propionic acid.
In the above-mentioned aqueous polyurethane (A) obtained by above-mentioned manufacture method, preferably using polycarbonate polyol as
Polycarbonate-based aqueous polyurethane obtained by raw material, this is due to the high reason of its coating strength.In addition, above-mentioned aqueous polyurethane
(A) may be used alone, two or more kinds can also be used.
Above-mentioned waterborne polyester (B) as long as be dissolved or dispersed in the polyester of aqueous medium, preferably water dispersible polyester
Resin.Water dispersible polyester resin is to impart the resin of water dispersible by introducing hydrophilic radical in polyester resin, is made
For commercially available product, such as can enumerate：" Vylonal " series of Toyo Boseki K.K etc..
The number-average molecular weight (Mn) preferably 5 of above-mentioned waterborne polyester (B), 000~500,000 scope, more preferably 10,000
~300,000 scope, further preferred 150,000~250,000 scope.In addition, the glass transition temperature of waterborne polyester
Spend (hereinafter referred to as " Tg ".) preferably -30~130 DEG C scope, more preferably -20~100 DEG C scope, further preferably -10
~80 DEG C of scope.Above-mentioned waterborne polyester (B) may be used alone, two or more kinds can also be used.
Above-mentioned aqueous acrylic resin (C) as long as be dissolved or dispersed in the acrylic resin of aqueous medium i.e.
Can, it can enumerate：Using acrylic monomer as main material, and what is polymerize in an aqueous medium using emulsifying agent utilizes breast
Aqueous acrylic resin's emulsion that liquid polymerize and produced；Using the acrylic monomer with carboxyl in organic solvent
After being polymerize, using in alkali and carboxyl, and it is scattered in an aqueous medium obtained by self-emulsifying aqueous acrylic resin etc..
As above-mentioned aqueous acrylic resin (C), can also use：With the carbamate after waterborne polyurethane modified
Modified aqueous acrylic acid resinoid, with various modified acrylic acids such as the modified water-based silica acrylic acid resinoids of silane compound
Resin.Above-mentioned aqueous acrylic resin (C) may be used alone, two or more kinds can also be used.
On the use level of above-mentioned aqueous polyurethane (A), waterborne polyester (B) and aqueous acrylic resin (C), relative to
Total preferably 5~60 mass parts of the mass parts of aqueous polyurethane (A) 100, waterborne polyester (B) and aqueous acrylic resin (C)
Scope, more preferably 10~50 mass parts scope, the scope of further preferred 20~45 mass parts, because can improve
Delustring sense, coating strength can be made abundant.
As above-mentioned delustering agent (D), such as can enumerate：Silicon dioxide granule, organic microbead, calcium carbonate, magnesium carbonate, carbonic acid
Barium, talcum, aluminium hydroxide, calcium sulfate, kaolin, mica, asbestos, mica (マ ィ カ), calcium silicates, aluminium hydrosilicate etc..
As above-mentioned silicon dioxide granule, can enumerate：Dry type silica, wet silicon dioxide etc..Wherein, preferred dry
Silica, because dispersion effect is high and the adjusting range of gloss number is wide.In addition, table is more preferably carried out by organic compound
Face modification after dry type silica because it is more readily dispersible in the composition.As the flat of these silicon dioxide granules
The scope of the scope of equal particle diameter, preferably 2~14 μm, more preferably 3~12 μm.
As the usage amount of above-mentioned silicon dioxide granule, relative to above-mentioned aqueous polyurethane (A), waterborne polyester (B) and water
The scope of the mass parts of total resin component 100, preferably 0.1~40 mass parts of property acrylic resin (C), more preferably 10~30
The scope of mass parts, because the gloss number for the appearance design that can obtain required matt state can be reached.
As above-mentioned organic microbead, such as can enumerate：Acrylic compounds microballon, carbamate microballon, silicon microballon, alkene are micro-
Pearl etc..
Above-mentioned delustering agent (D) may be used alone, two or more kinds can also be used.
As above-mentioned crosslinking agent (E), can enumerate：Oxazoline, carbodiimide, polyisocyanates, blocked isocyanate, ring
The Lauxite such as oxygen, polysiloxanes, aziridine, alkylated melamine system crosslinking agent, hydrazides system crosslinking agent etc..Wherein, from friendship
From the aspect of joining performance and security, preferred carbodiimide.In addition, these crosslinking agents (E) can be used alone, can also be 2 kinds
It is used in combination above.As above-mentioned crosslinking agent (E) usage amount, from the viewpoint of coating strength, relative to above-mentioned aqueous polyurethane
(A), the mass parts of total resin component 100 of waterborne polyester (B) and aqueous acrylic resin (C), preferably 0.5~30 mass parts
Scope, more preferably 2~25 mass parts scope.
Except above-mentioned aqueous polyurethane (A), waterborne polyester (B), aqueous acrylic resin (C), delustering agent (D) and crosslinking agent
(E) polyolefin-wax (F) can also be coordinated beyond, in aqueous surface-treating agent of the invention.
In said polyolefins wax (F), preferably its fusion range is 140~180 DEG C of polyolefin-wax, and more preferably it melts model
The polyolefin-wax for 145~175 DEG C is enclosed, the polyolefin-wax that its further preferred fusion range is 150~170 DEG C, because
Even if alcohol equal solvent touches film, the vestige (solvent trace) of residual alcohol equal solvent is not easy to, solvent resistance improves.As so
Polyolefin-wax (F), Tissuemat E, polypropylene wax etc. can be enumerated.These polyolefin-waxes (F) can be used alone, can also be 2 kinds
It is used in combination above.In addition, in the present invention, as polyolefin-wax (F), and with it is of more than two kinds in the case of, its fusion range refers to mix
The fusion range of compound.In addition, fusion range is based on JIS test methods K0064-1992 and measured.
In said polyolefins wax (F), preferably using polypropylene wax as the polyolefin-wax of principal component, because can reduce
Solvent trace.In addition, the usage amount as said polyolefins wax (F), relative to above-mentioned aqueous polyurethane (A), waterborne polyester (B) and
The mass parts of total resin component 100 of aqueous acrylic resin (C), the preferably scope of 0.1~20 mass parts, more preferably 3~
The scope of 15 mass parts, because the reducing effect and coating strength of solvent trace can be improved.
In addition to mentioned component (A)~(F), various surface-actives can also be coordinated in aqueous surface-treating agent of the invention
Agent, defoamer, levelling agent, viscoplasticity regulator, defoamer, wetting agent, dispersant, preservative, film forming agent, plasticizer, it is impregnated with
Agent, spices, bactericide, acaricide, mould inhibitor, ultra-violet absorber, antioxidant, antistatic agent, fire retardant, dyestuff, pigment
Additives such as (such as titanium white, Indian red, phthalocyanine, carbon black, permanent yellows etc.).
The article of the present invention has the film of the aqueous surface-treating agent of the present invention.In addition, as article, such as can lift
Go out：Housing, the electronic equipment (computer, portable phone, smart mobile phone etc.) of family's electrical article (refrigerator, washing machine, air-conditioning, TV etc.)
Housing, the material of musical instrument (piano, electronic organ, electronic musical instrument etc.)；The built-in material of automobile or rail truck (instrument board, door
Plaque, ceiling, compartment drop cloth etc.), (wallpaper, three-ply board are glued with cosmetic sheet, steel plate with cosmetic sheet, chair for building materials or furniture material
Patch leather etc.), the formed products such as packaging material (packaging film etc.)；Wood materials (three-ply board, glued board, individual layer stacking material
Material etc.)；Ceramic material (built-in ceramic tile, brick etc.).It can enumerate：Move (skiing, archery, golf, tennis etc.) apparatus material；
Footwear materials (upper materials of footwear, bottom, core, heel, the rear root face of footwear, shoe-pad etc.)；Metal material (iron, copper, zinc, aluminium etc.)
Deng.In these articles, aqueous surface-treating agent of the invention can be suitable for formed products, be preferred for the formed products
In TPO leathers, TPO pieces.
Embodiment
Hereinafter, the present invention is further illustrated by embodiment.
(embodiment 1)
Following compositions are uniformly mixed, obtain aqueous surface-treating agent (1).The composition is：(DIC is public for aqueous polyurethane
Department system " HYDRAN WLS-210 ", polycarbonate-based aqueous polyurethane, nonvolatile component：35 mass %) 49 mass parts are (as water
Property polyurethane, be 17.15 mass parts), (" Vylonal MD-1100 ", moisture dissipate poly- Toyo Boseki K.K's system waterborne polyester
Ester resin, number-average molecular weight：20000, Tg：40 DEG C, nonvolatile component：30 mass %) 15.3 mass parts (as waterborne polyester, are
4.59 mass parts), crosslinking agent (Nisshinbo KCC system " CARBODILITE E-04 ", carbodiimide system crosslinking agent)
(EVONIK DEGUSSA company systems " ACEMATT3300 ", by dry process manufacture and surface is by organic for 4.2 mass parts, delustering agent
Silicon dioxide granule after processing, average grain diameter：9.5 μm) 4 mass parts, polypropylene wax (Micro Powders company systems
“MICROMATTE 1213UVW”；150~156 DEG C of fusion range) 1.4 mass parts, nonionic surfactants (first industry
Pharmaceutical Co., Ltd's system " NOIGEN EA-157 ") 0.1 mass parts, fluorine system surfactant (DIC company systems " Mega Fac F-
444 ") 0.1 mass parts, viscoplasticity regulator (SAN NOPCO company systems " 612NC of SN シ Star Network Na one ") 0.9 mass parts and from
The sub- mass parts of exchanged water 25.
[making of sample for evaluation]
The aqueous surface-treating agent (1) obtained in above-mentioned record is coated in TPO piece (thickness using bar coater No.14
On 0.4mm), then dried 1 minute at 120 DEG C, obtain sample for evaluation.
[making of vacuum forming product]
Using vacuum former (into light Industry Co., Ltd system " vacuum former FORMING300X "), to above-mentioned record
In obtained sample for evaluation carry out vacuum forming so that reaching 350% in terms of area ratio, obtain vacuum forming product.
[measure of gloss number]
For the film coated surface of the aqueous surface-treating agent of sample for evaluation obtained in above-mentioned record, gloss meter is used
(KONICA MINOLTA OPTICS, INC. systems " GM-268Plus ") respectively determine vacuum forming before and vacuum forming after 60 °
Gloss number.
[evaluation of shaping processability]
Calculate 60 ° of gloss numbers of the film coated surface of the aqueous surface-treating agent before and after the vacuum forming determined in above-mentioned record
Rate of change, according to following benchmark evaluation shaping processabilities.In addition, the rate of change of 60 ° of gloss numbers is calculated by following formula (1).
A：Rate of change is less than 50%.
B：Rate of change is 50% less than 100%.
C：Rate of change is more than 100%.
(embodiment 2)
The waterborne polyester used in embodiment 1 is changed to waterborne polyester (Toyo Boseki K.K system " Vylonal
MD-1200 ", water dispersible polyester resin, number-average molecular weight：1.5 ten thousand, Tg：67 DEG C, nonvolatile component：34 mass %) 13.5 mass
Part (being 4.59 mass parts as waterborne polyester), 26.8 mass parts are changed to by the use level of ion exchange water, in addition,
Carry out similarly to Example 1, obtain aqueous surface-treating agent (2).
(embodiment 3)
The waterborne polyester used in embodiment 1 is changed to waterborne polyester (Toyo Boseki K.K system " Vylonal
MD-1480 ", water dispersible polyester resin, number-average molecular weight：1.5 ten thousand, Tg：20 DEG C, nonvolatile component：25 mass %) 18.4 mass
Part (being 4.6 mass parts as waterborne polyester), 21.9 mass parts are changed to by the use level of ion exchange water, in addition, with
Embodiment 1 is similarly carried out, and obtains aqueous surface-treating agent (3).
(embodiment 4)
The waterborne polyester used in embodiment 1 is changed to waterborne polyester (Toyo Boseki K.K system " Vylonal
MD-1930 ", water dispersible polyester resin, number-average molecular weight：20000, Tg：- 10 DEG C, nonvolatile component：31 mass %) 14.8 mass
Part (being 4.59 mass parts as waterborne polyester), 25.5 mass parts are changed to by the use level of ion exchange water, in addition,
Carry out similarly to Example 1, obtain aqueous surface-treating agent (4).
(embodiment 5)
The waterborne polyester used in embodiment 1 is changed to aqueous acrylic resin's (Toagosei Co., Ltd's system
" CIRRUS PC-751 ", water-based silica acrylic acid resinoid, nonvolatile component：45 mass %) 15.3 mass parts are (as water-based third
Olefin(e) acid resinoid, it is 7.02 mass parts), the use level of ion exchange water is changed to 25 mass parts, in addition, with embodiment
1 is similarly carried out, and obtains aqueous surface-treating agent (5).
(embodiment 6)
The waterborne polyester used in embodiment 1 is changed to aqueous acrylic resin (Dainippon Ink Chemicals system " VONCOAT
HY-364 ", urethane-modified aqueous acrylic resin, nonvolatile component：45 mass %) 10.2 mass parts are (as water
Property acrylic resin, is 4.59 mass parts), the use level of ion exchange water is changed to 30.1 mass parts, in addition, with
Embodiment 1 is similarly carried out, and obtains aqueous surface-treating agent (6).
(embodiment 7)
The waterborne polyester used in embodiment 1 is changed to aqueous acrylic resin (Dainippon Ink Chemicals system " VONCOAT
VF-1040 ", aqueous acrylic resin's emulsion, nonvolatile component：50 mass %) 9.2 mass parts are (as water-borne acrylic type
Resin, it is 4.6 mass parts), the use level of ion exchange water is changed to 31.1 mass parts, in addition, similarly to Example 1
Ground is carried out, and obtains aqueous surface-treating agent (7).
(comparative example 1)
Following compositions are uniformly mixed, obtain aqueous surface-treating agent (R1).The composition is：Aqueous polyurethane (DIC strains
Formula commercial firm system " HYDRANWLS-210 ", polycarbonate-based aqueous polyurethane, nonvolatile component：35 mass %) 60.9 mass parts
(being 21.3 mass parts as aqueous polyurethane), crosslinking agent (Nisshinbo KCC system " CARBODILITE E-04 ",
Carbodiimide system crosslinking agent) 4.2 mass parts, delustering agent (EVONIK DEGUSSA company systems " ACEMATT 3300 ", by dry process
Manufacture and silicon dioxide granule of the surface after organic process, average grain diameter：9.5 μm) 4 mass parts, polypropylene wax (Micro
Powders company systems " MICROMATTE 1213UVW "；150~156 DEG C of fusion range) 1.4 mass parts, nonionic system surface live
Property agent (Di-ichi Kogyo Seiyaku Co., Ltd.'s system " NOIGEN EA-157 ") 0.1 mass parts, fluorine system surfactant (DIC strain formula meetings
Society's system " Mega Fac F-444 ") 0.1 mass parts, viscoplasticity regulator (SAN NOPCO company systems " SN シ Star Network Na one
612NC ") 0.9 mass parts and the mass parts of ion exchange water 28.4.
For aqueous surface-treating agent (2)~(7) obtained in above-described embodiment 2~7 and comparative example 1 and (R1), with reality
Apply example 1 similarly to operate, carry out the evaluation of the measure and formability of 60 ° of gloss numbers.
Aqueous surface-treating agent (1)~(7) that are obtained in above-described embodiment 1~7 and comparative example 1 and (R1) with charge-coupled
Evaluation result into, the measure of 60 ° of gloss numbers and formability is as shown in table 1.
[table 1]
It was found from the result shown in table 1, the aqueous surface-treating agent for the present invention is the aqueous surface of embodiment 1~7
For inorganic agent (1)~(7), the rates of change of its 60 ° of gloss numbers is less than 57%, with low uncertainty, though carry out with stretching into
Shape is processed, and the change of the delustring sense of film coated surface is also few, and shaping processability is good.
On the other hand understand, comparative example 1 for it is unmated in the present invention together with aqueous polyurethane (A) and it is water-based gather
Ester (B) or the example of aqueous acrylic resin (C), the rate of change of its 60 ° of gloss numbers is 711%, and change is very big, and shaping adds
Work is insufficient.
Claims (6)
- A kind of 1. formed products aqueous surface-treating agent for the thermoplastic olefin for being applied in stretch forming processing, it is characterised in thatContaining aqueous polyurethane (A), delustering agent (D) and crosslinking agent (E), also containing waterborne polyester (B) or water-borne acrylic type tree Fat (C), wherein,Relative to the mass parts of the aqueous polyurethane (A) 100, the waterborne polyester (B) or the aqueous acrylic resin (C) Contain 5~60 mass parts.
- 2. the formed products of the thermoplastic olefin as claimed in claim 1 for being applied in stretch forming processing are handled with aqueous surface Agent, wherein,The aqueous polyurethane (A) is polycarbonate-based aqueous polyurethane.
- 3. the formed products of the thermoplastic olefin as claimed in claim 1 or 2 for being applied in stretch forming processing are with aqueous surface Agent is managed, wherein,The crosslinking agent (E) is carbodiimide.
- 4. the formed products of the thermoplastic olefin as claimed in claim 1 or 2 for being applied in stretch forming processing are with aqueous surface Agent is managed, it also contains polyolefin-wax (F).
- 5. the formed products of the thermoplastic olefin as claimed in claim 3 for being applied in stretch forming processing are handled with aqueous surface Agent, it also contains polyolefin-wax (F).
- A kind of 6. formed products, it is characterised in thatIt is the formed products with the thermoplastic olefin according to any one of claims 1 to 5 for being applied in stretch forming processing With the formed products of the film of aqueous surface-treating agent, and the formed products have been applied in stretch forming processing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013075926 | 2013-04-01 | ||
| JP2013-075926 | 2013-04-01 | ||
| PCT/JP2014/057284 WO2014162868A1 (en) | 2013-04-01 | 2014-03-18 | Aqueous surface treating agent and articles using same |
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| Publication Number | Publication Date |
|---|---|
| CN105073921A CN105073921A (en) | 2015-11-18 |
| CN105073921B true CN105073921B (en) | 2018-04-06 |
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| CN201480017380.8A Active CN105073921B (en) | 2013-04-01 | 2014-03-18 | Aqueous surface-treating agent and the article for having used the aqueous surface-treating agent |
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| JP (2) | JPWO2014162868A1 (en) |
| CN (1) | CN105073921B (en) |
| WO (1) | WO2014162868A1 (en) |
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| CN104673072B (en) * | 2014-10-14 | 2020-03-31 | 深圳瑞欧光技术有限公司 | Explosion-proof light-transmitting glass paint for lamps and preparation method thereof |
| JP2016084400A (en) * | 2014-10-24 | 2016-05-19 | Dic株式会社 | Aqueous resin composition, aqueous surface treatment agent and article using the same |
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| JP2000238183A (en) * | 1999-02-25 | 2000-09-05 | Mitsubishi Polyester Film Copp | Metallized film |
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| JP4203781B2 (en) * | 1999-04-13 | 2009-01-07 | 東洋紡績株式会社 | Polyester-based coating film |
| US6362270B1 (en) * | 1999-08-12 | 2002-03-26 | The Dow Chemical Company | Thermoplastic compositions for durable goods applications |
| US6878771B2 (en) * | 2002-09-30 | 2005-04-12 | Bhaskar R. Urs | Matte-finish polyurethane coating composition |
| JP2007262248A (en) * | 2006-03-29 | 2007-10-11 | Seikoh Chem Co Ltd | Water-based matte coating agent |
| SI2488563T1 (en) * | 2009-10-15 | 2015-08-31 | Bayer Intellectual Property Gmbh | Use of nmp-free coatings for automotive interiors |
| JP5434605B2 (en) * | 2010-01-06 | 2014-03-05 | 東洋紡株式会社 | Easy-adhesive white polyester film |
| JP5769382B2 (en) * | 2010-03-31 | 2015-08-26 | 本田技研工業株式会社 | Synthetic resin leather and method for producing the same |
| JP6036111B2 (en) * | 2012-09-28 | 2016-11-30 | Dic株式会社 | Aqueous surface treatment agent and article using the same |
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| WO2014162868A1 (en) | 2014-10-09 |
| JP5790895B2 (en) | 2015-10-07 |
| JPWO2014162868A1 (en) | 2017-02-16 |
| CN105073921A (en) | 2015-11-18 |
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