WO1998034991A1 - Emulsion de resine de peinture resistant aux intemperies - Google Patents

Emulsion de resine de peinture resistant aux intemperies Download PDF

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Publication number
WO1998034991A1
WO1998034991A1 PCT/US1998/000600 US9800600W WO9834991A1 WO 1998034991 A1 WO1998034991 A1 WO 1998034991A1 US 9800600 W US9800600 W US 9800600W WO 9834991 A1 WO9834991 A1 WO 9834991A1
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WO
WIPO (PCT)
Prior art keywords
group
resin
monomer containing
resin emulsion
paint
Prior art date
Application number
PCT/US1998/000600
Other languages
English (en)
Inventor
Hiroshi Ide
Motoyuki Takagi
Original Assignee
National Starch And Chemical Investment Holding Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Starch And Chemical Investment Holding Corporation filed Critical National Starch And Chemical Investment Holding Corporation
Priority to US09/155,271 priority Critical patent/US6251986B1/en
Priority to EP98903463A priority patent/EP0896608A1/fr
Publication of WO1998034991A1 publication Critical patent/WO1998034991A1/fr

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Classifications

    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • the present invention relates to a paint resin emulsion for use as an aqueous painter binder having improved weatherability. More particularly, the invention provides a resin emulsion having improved resistance against degradation due to exposure to ultra-violet or visible light.
  • the resin emulsion according to the present invention will find a variety of applications including, but not limited to, application as a binder to be contained in paint for domestic electric appliances, steel-made machinery, large construction works, automobiles, building constructions, building materials, wood materials or the like. In recent years, in consideration of the environmental pollution or effect on human body, there has been a general shift from solvent-based paint to water-based paint.
  • water-based or aqueous paint using an acrylic resin emulsion as a binder has been often used because it satisfies the requirements as paint resin such as paint-film forming ability, adhesion to the substrate, pigment dispersion stability or the like.
  • fluorine resin, silicone resin or the like has been put into use as paint resin having improved long-term weatherability capable of retaining gloss as long as 4000 to 5000 hours as determined in the accelerated weathering test using the sunshine weather meter.
  • the fluorine resin and the silicone resin are inferior to the acrylic resin in the respect of such properties as gloss, pigment dispersion stability.
  • the primary object of the present invention is to provide improved acrylic resin which has the gloss-retaining ability almost as good as that of the fluorine resin or silicone resin while maintaining the advantages of conventional acrylic resin paint binder such as the gloss-retaining ability or pigment dispersion stability.
  • the paint resin emulsion having improved weatherability comprises in 100 wt.% of the resin component in the emulsion thereof:
  • the light stabilizing group contained in such a monomer containing the light stabilizing group may be an amino group of a hydroxyl group surrounded by a bulky substituent having steric hindering effect, i.e. a functional group commonly referred to as a hindered amino group or hindered hydroxyl group.
  • a functional group commonly referred to as a hindered amino group or hindered hydroxyl group.
  • the construction of claim 1 further comprises the additional component (c), i.e. 0.1 to 10 wt.% of a monomer containing ultra-violet absorbent group.
  • Such a monomer containing the ultra-violet absorbent group as this component (c) is a compound capable of contributing to further improvement of weatherability by absorbing ultra-violet ray which can excite and cut off the chemical bond of the resin molecules. Then, by addition of this further component (c), the weatherability may be further improved.
  • the amount of the component (c) is smaller than the lower limit of 0.1 wt.%, the component cannot provide its effect sufficiently and an amount thereof greater than 10 wt.% will only result in cost increase, without providing any additional effect.
  • a monomer containing the light stabilizing group is represented by the following chemical formula (chemical formula 4):
  • X is a nitrogen atom, there is provided an amino group, which may be either -NH- or -NR-(R is lower alkyl group). It is believed that the improvement of the weatherability is attributable mainly to the nitrogen atom to which R 4 of the compound represented by the above chemical formula 4 is an alkyl group.
  • a monomer containing the alkoxysilyl group is represented by the following chemical formula (chemical formula 5):
  • R 5 is H or CH 3 ;
  • R 6 is an alkyl group having a carbon number ranging between 1 and 3;
  • Y is an alkylene group having a carbon number ranging between 1 and 6).
  • a monomer containing the ultra-violet absorbent group employed in the present invention is represented by the following chemical formula (chemical formula 6):
  • R 7 is H or CH 3 ;
  • Z is an alkylene group having a carbon number ranging between 1 and 6).
  • the weatherability of the resin emulsion of the invention may be significantly improved through absorption of ultra-violet ray due to the conjugated double bond in the molecule represented by the formula 6 in combination with the above-described effect of the monomer containing the light stabilizing group.
  • the component (a) which may be employed preferably as the monomer containing the light stabilizing group in the present invention illustratively includes esters or amides formed from acrylic acid, methacrylic acid, or crotonic acid with hydroxyl group or amino group of: 4-hydroxy- 2,2,6,6-tetramethylpiperizine; 4-amino-2,2,6,6-tetramethylpiperizine; 4- hydroxy-1 ,2,2,6,6-pentamethylpiperizine; 4-amino-1 , 2,2,6, 6-pentamethyl-pi- perizine; 4-amino-4-cyano-2,2,6,6-tetramethylpiperizine; 1 -(metha)acryloy I-4- hydroxy-2,2,6,6-tetramethylpiperizine; 1-crotonoyl-4-hydroxy-2,2,6,6-tetra- methylpiperizine, and so on. These compounds may be used singly or in combination of two or more members.
  • the component (b) which may be employed preferably as the monomer containing the alkoxysilyl group illustratively includes: vinyltrimethoxysilane; vinyltriethoxysilane; vinyltris ( ⁇ -methoxyethoxy) silane; ⁇ -methacryloxypropyltrimethoxysilane and so on.
  • ⁇ - methacryloxypropyltrimethoxysilane a monomer, in which R 5 is CH 3 and R 6 is methyl group, and Y is CH 2 -CH 2 -CH 2 -(propylene group) in the chemical formula 5 specified above, is preferred in the respects of performances, cost and so on.
  • the (metha)acrylic monomer refers to monomers including either one or both of derivatives based on acrylic acid and derivatives based on methacrylic acid.
  • copolymerization with other ultra-violet absorbent monomers for improving durability against ultra-violet ray exposure are also preferred.
  • monomers 2-hydroxy-4-[3-(metha) acryloxy-2- hydroxypropoxy] benzophenone, 2,2'-dihydroxy-4-[3-(metha)acryloxy-2- hydroxypropoxy] benzophenone and so on, may be cited.
  • Typical examples of the (metha) acrylic acid monomer are acrylic acid alkyl ester, and methacrylic acid alkyl ester. More specifically, the following compounds may be cited.
  • acrylic acid alkyl ester it is possible to employ methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethyhexyl acrylate, isobornyl acrylate and so on.
  • methacrylate (ester) it is possible to use methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate and so on. These compounds may be used singly or in combination of two or more members.
  • Monomers other than the (metha)methacrylate monomers may be also used as raw material of the paint resin of the present invention depending on the necessity. Specifically, the following monomers may be cited: (1 ) aromatic monomers such as styrene, vinyl toluene, ⁇ -methyl- styrene and so on,
  • halogen-containing monomers such as vinyl chloride, viny dene chloride or the like, (4) vinyl ethers,
  • cyano group-containing monomers such as acrylonitnle or the like
  • nitrogen-containing monomers such as N-dimethylaminoethyl (metha) acrylate, 4-v ⁇ nylpy ⁇ d ⁇ ne, vinylimidazole, and so on
  • a monomer which may contribute to the formation of cross linking structure such as divinylbenzene, diallyl phthalate, ethylene glycol dimethacrylate or the like
  • use of the aromatic monomer, styrene in particular it is preferred due to lower cost, good compatibility with the other components, contribution to improvement of the water resistance of the resultant film and the like
  • monomers having such functional group as OH group, COOH group, sulfonic acid group or the like may be copolyme ⁇ zed also
  • monomers containing functional group the following may be cited a) monomers containing OH group hydroxyethyl (metha)acrylate, hydroxylpropyl (metha) acrylate, allyl alcohol, caprolactone modified hydroxy (metha) acrylate (manufactured by Daicel Chemical Industries Ltd.), mono (metha) acrylate of bishydroxyethyl phthalate; b) mononomers containing COOH group: acrylic acid, methacrylate acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, and so on; c) monomers containing sulfonic acid: vinyl sulfonic acid, styrene sulfonic acid, sulfoethyl (metha) acrylate and so on; d) acidic phosphate monomers: 2-(metha)acryloyloxyethyl acid phosphate; 2-(metha)acryloyloxypropyl acid phosphate;
  • any of those well-known in the art may be employed. Specifically, water-insoluble initiators such potassium persulfate, ammonium persulfate or the like are preferred. Yet, water-insoluble initiators such as azobisisobutylotrile, benzoyl peroxide, ME peroxide, t-butylhydroperoxide or the like may be employed also. Further, redox type catalyst comprising e.g. a combination of radical generator and a sulfite may be employed as well. Moreover, these persulfates, peroxide in combination with metal ions, and reducing agents such as L-ascorbic acid, L-sorbic acid and so on may be employed also.
  • chain transfer agents be used for molecular weight adjustment.
  • any compounds well-known in the art may be employed as such chain transfer agent. Typical examples are mercaptans such as n-dodecyl mercaptan, laurylmethyl mercaptan and so on
  • emulsifiers may be employed, depending on the necessity as such emulsifier, surfactants well-known in the art may be used Also, for forming protective colloid, water-soluble polymer may be used And, it is also preferred that such compounds illustratively include cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose or the like and there may be used such compounds for forming the protective colloid including water-soluble polyurethane resin, water-soluble acrylic resin, polyvinyl pyrrolydone, polyvinyl alcohol and the like
  • additive type anti-weathering agent as the light stabilizing agent, ultra-violet absorbent, or anti-oxidizing agent
  • additive type anti-weathering agents will gradually bleed out as described hereinbefore and will effuse due to rain or the like Therefore, these agents will not contribute to improvement of long-term weatherability, but will be effective at an earlier time In particular, these agents can be expected to achieve an 'auxiliary effect' for prolonging the effect of the above- described monomer unit having the anti-weathering agent copolyme ⁇ zed into the resin emulsion
  • the method of synthesizing the resin emulsion is as follows. Incidentally, in the following discussion, the weight parts will be represented simply as 'parts'.
  • New Frontier A-229E manufactured by Dia-ichi Kogyo Seiyaku Co. Ltd.
  • component (a) of the invention (a-1) 4-methaclyoxy-2,2,6,6- tetramethylpiperidinyl methacrylate and (a-2) N-methyl-2,2,6,6- tetramethylpiperidinyl methacrylate were used; and as the component (b), (b- 1) ⁇ -methacryloxypropyltrimethoxysilane was employed; and as the component (c), 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole was used, respectively.
  • Table 1 Table 1
  • paint was prepared according to the composition shown in the following Table 2.
  • HEC SP-600 (Daicel Chemical Industries 0.1 part
  • the resultant emulsion was applied on a slate plate so as to be a dry film in about 100 ⁇ m thickness. And, this was dried for 7 (seven) days at 50°C, thus a test piece was obtained. Then, this test piece was subjected to an exposure test using the sunshine weather meter. After the lapse of 300 hours, the condition of the film was evaluated for the gloss-retaining ratio (%) using a gloss meter and the discoloration resistance: ⁇ E, was evaluated using a differential colorimeter, respectively.
  • the present invention there has been achieved a paint resin emulsion capable of forming paint film having superior gloss-retaining ability and anti-discoloring ability exhibited in the exposure test using the sunshine weather meter while achieving also the solution resistance, cracking resistance and blister resistance all to satisfactory levels. Further, the paint using the resin emulsion of the present invention is superior also in the workabilities such as the pigment dispersion stability, applicability or building performance.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une résine acrylique présentant des qualités de résistance aux intempéries, et notamment de maintien de l'éclat se comparant à ce qu'on obtient avec les fluororésines ou les résines siliconiques, tout en conservant les qualités que l'on constate en matière d'éclat et de stabilité de la dispersion pigmentaire en utilisant comme résine de peinture un liant conventionnel à la résine acrylique. L'émulsion est caractérisée en ce qu'elle contient, en masse rapportée au composant émulsion résinique, (a) de 0,1 à 10 % d'un monomère contenant un groupe photostabilisant, et (b) de 0,1 à 10 % d'un monomère contenant un groupe alcoxysilyl. De préférence, elle contient également (c) de 0,1 à 10 % d'un monomère contenant un groupe absorbant l'ultraviolet.
PCT/US1998/000600 1997-02-07 1998-01-07 Emulsion de resine de peinture resistant aux intemperies WO1998034991A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US09/155,271 US6251986B1 (en) 1997-02-07 1998-01-07 Paint resin emulsion having weatherability
EP98903463A EP0896608A1 (fr) 1997-02-07 1998-01-07 Emulsion de resine de peinture resistant aux intemperies

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/24657 1997-02-07
JP2465797A JPH10219140A (ja) 1997-02-07 1997-02-07 耐候性塗料用樹脂エマルション

Publications (1)

Publication Number Publication Date
WO1998034991A1 true WO1998034991A1 (fr) 1998-08-13

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Family Applications (1)

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PCT/US1998/000600 WO1998034991A1 (fr) 1997-02-07 1998-01-07 Emulsion de resine de peinture resistant aux intemperies

Country Status (4)

Country Link
EP (1) EP0896608A1 (fr)
JP (1) JPH10219140A (fr)
CA (1) CA2251706A1 (fr)
WO (1) WO1998034991A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000020523A1 (fr) * 1998-10-05 2000-04-13 Nippon Shokubai Co., Ltd. Materiau stratifie en resine absorbant les ultraviolets
US6677047B2 (en) * 2000-02-04 2004-01-13 Shin-Etsu Chemical Co., Ltd. Coating composition, coating method, and coated article

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001114841A (ja) * 1999-10-21 2001-04-24 Nippon Shokubai Co Ltd 紫外線吸収性共重合体および該共重合体からなる薄膜、並びに該薄膜を含む多層積層体
JP2001213060A (ja) * 2000-02-01 2001-08-07 Uchu Kankyo Kogaku Kenkyusho:Kk 印刷物保護被膜組成物およびこれを用いた印刷物保護シート並びに印刷表面の保護方法
JP2001323209A (ja) * 2000-05-12 2001-11-22 Mitsubishi Rayon Co Ltd 水性被覆組成物
EP1507826A4 (fr) 2002-05-17 2007-11-07 Othera Pharmaceuticals Inc Amelioration de l'evolution des cataractes et d'autres maladies ophtalmiques
US7825134B2 (en) 2003-05-19 2010-11-02 Othera Holding, Inc. Amelioration of cataracts, macular degeneration and other ophthalmic diseases
JP5266100B2 (ja) * 2009-03-05 2013-08-21 ケイミュー株式会社 着色基材
KR101921776B1 (ko) * 2011-05-30 2018-11-23 미쯔비시 케미컬 주식회사 성형 재료 및 성형체
CN103596994B (zh) * 2011-05-31 2016-02-17 三菱丽阳株式会社 固化用组合物和聚合物
JP6497695B2 (ja) * 2014-11-25 2019-04-10 関西ペイント株式会社 常温硬化性の耐候性塗料組成物
JP6497697B2 (ja) * 2015-01-30 2019-04-10 関西ペイント株式会社 常温硬化性の耐候性塗料組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0475149A2 (fr) * 1990-09-10 1992-03-18 Nippon Arc Co., Ltd. Composition de revêtement et articles de résin ainsi enduites
JPH0726155A (ja) * 1993-07-12 1995-01-27 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JPH08325488A (ja) * 1995-05-30 1996-12-10 Dainippon Toryo Co Ltd 艶消し電着塗料組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0475149A2 (fr) * 1990-09-10 1992-03-18 Nippon Arc Co., Ltd. Composition de revêtement et articles de résin ainsi enduites
JPH0726155A (ja) * 1993-07-12 1995-01-27 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JPH08325488A (ja) * 1995-05-30 1996-12-10 Dainippon Toryo Co Ltd 艶消し電着塗料組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 126, no. 12, 24 March 1997, Columbus, Ohio, US; abstract no. 158809, XP002065450 *
DATABASE WPI Section Ch Week 9514, Derwent World Patents Index; Class A14, AN 95-102073, XP002065451 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000020523A1 (fr) * 1998-10-05 2000-04-13 Nippon Shokubai Co., Ltd. Materiau stratifie en resine absorbant les ultraviolets
US6372355B1 (en) * 1998-10-05 2002-04-16 Nippon Shokubai Co., Ltd. Ultraviolet absorptive laminated resinous article
US6677047B2 (en) * 2000-02-04 2004-01-13 Shin-Etsu Chemical Co., Ltd. Coating composition, coating method, and coated article
US6855768B2 (en) 2000-02-04 2005-02-15 Shin-Etsu Chemical Co., Ltd. Coating composition, coating method, and coated article

Also Published As

Publication number Publication date
JPH10219140A (ja) 1998-08-18
CA2251706A1 (fr) 1998-08-13
EP0896608A1 (fr) 1999-02-17

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