WO2020175860A1 - 프라이머 조성물 - Google Patents

프라이머 조성물 Download PDF

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Publication number
WO2020175860A1
WO2020175860A1 PCT/KR2020/002554 KR2020002554W WO2020175860A1 WO 2020175860 A1 WO2020175860 A1 WO 2020175860A1 KR 2020002554 W KR2020002554 W KR 2020002554W WO 2020175860 A1 WO2020175860 A1 WO 2020175860A1
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WO
WIPO (PCT)
Prior art keywords
primer composition
epoxy resin
monomer
weight
acrylate monomer
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2020/002554
Other languages
English (en)
French (fr)
Inventor
이정현
이재영
김유석
권진욱
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KCC Corp
Original Assignee
KCC Corp
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 KCC Corp filed Critical KCC Corp
Priority to CN202080010148.7A priority Critical patent/CN113348218B/zh
Priority to EP20762100.4A priority patent/EP3933004B1/en
Priority to SG11202107411XA priority patent/SG11202107411XA/en
Publication of WO2020175860A1 publication Critical patent/WO2020175860A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing 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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a primer composition.
  • an adhesive is applied to the adhesion between the vehicle body and the window of an automobile, but there are many cases where sufficient adhesion cannot be obtained by using only the adhesive. In such a case that sufficient adhesion cannot be obtained by using the adhesive alone, the adhesive surface is preliminarily applied. After the primer composition is applied, adhesives are applied on it to ensure sufficient adhesion.
  • a silane coupling agent to a binder component such as polyester polyurethane or acrylic resin as the main material of the primer used in the past,
  • isocyanate groups react with moisture in the atmosphere and the activity of the primer surface is impaired, there is a problem in that workability or reworkability is poor, such as reapplying to obtain sufficient adhesion.
  • isocyanate-based automotive primers have problems with silicon. There were also problems such as not being able to obtain sufficient adhesion for hard-coated glass.
  • the present invention is for conventional isocyanate-based urethane adhesives.
  • the present invention is a silane type containing at least two amino groups or imino groups.
  • Alkoxysilane polymer containing units derived from monomers and units derived from trialkoxysilane-based monomers; from non-functional acrylate monomers 2020/175860 1»(:1 ⁇ 1 ⁇ 2020/002554 Acrylic resin containing at least one selected from the derived units; and epoxy resins; and primer compositions are provided.
  • the primer composition of this invention is derived from a trialkoxysilane-based monomer
  • a primer By using an acrylic resin containing at least one selected from a unit derived from a unit derived from a silane-based monomer containing a unit and at least two amino groups or imino groups, and a unit derived from a non-functional acrylate monomer, a primer
  • the adhesion of the primer can be improved, and the above primer composition is excellent in storage stability and weather resistance, but also has excellent storage stability and workability after primer application due to a long housekeeping time. In particular, it has excellent adhesion to glass as well as automobile bodies (especially at low temperatures). Adhesiveness) has excellent effects.
  • the present invention provides a primer composition.
  • the primer composition of the present invention is an alkoxysilane polymer; an acrylic resin; and an epoxy
  • Susie includes.
  • the alkoxysilane polymer contained in the primer composition of the present invention plays a role in improving the adhesion to the primer plastic or adhesive (311 (0 urine (3: 11 1 11 ⁇ )).
  • the alkoxysilane polymer may include a unit derived from a silane-based monomer containing at least two amino groups or imino groups, and a unit derived from a trialkoxysilane-based monomer. That is, the alkoxysilane polymer is, the amino group or the amino group or a unit derived from a trialkoxysilane-based monomer.
  • One or more monomers selected from silane-based monomers containing at least two imino groups, and one or more monomers selected from the trialkoxysilane-based monomers may be polymerized or prepared by copolymerization.
  • the trialkoxysilane-based monomer is a trialkoxy group substituted at the terminal
  • trialkoxysilane-based monomer may include at least one functional group selected from an acrylic group, a mercapto group, and a glycidyl group.
  • the trialkoxysilane monomer is 3 -methacryloyloxypropyltrimethoxysilane, 3 -methacryloyloxypropyltriethoxysilane,
  • the silane-based monomer containing at least two amino groups or imino groups is not limited thereto, as long as it can form an alkoxysilane polymer by polymerization reaction with the trialkoxysilane-based monomer, and includes at least two of the amino groups or imino groups.
  • the silane-based monomer may be substituted with a trialkoxy group at the terminal.
  • a silane-based monomer containing at least two amino groups or imino groups is
  • trialkoxy group When a trialkoxy group is substituted at the terminal, it may differ from the trialkoxysilane-based monomer described above.
  • Dimethoxysilane (N-beta-(Aminoebi iyl)-gamma-aminopropylmebi iyl dimethoxy silane), etc., for example, may include a triaminofucntional silane containing at least three amino groups or imino groups. have.
  • a trialkoxysilane monomer and a silane monomer containing at least two amino groups or imino groups may include an alkoxysilane polymer obtained by reacting in a weight ratio of greater than 1:1 and less than 5:1, for example, greater than 1:1 and 4 : It may include an alkoxysilane polymer obtained by reaction in a weight ratio of 1 or less.
  • the primer and the silane monomer containing at least two amino groups or imino groups are 1:1 or less.
  • the adhesion with the adhesive (DGU) is deteriorated, and if it exceeds 5:1, the storage performance may be poor.
  • the weight average molecular weight of the alkoxysilane polymer may be 700 to 5,000 g/mol
  • the weight average molecular weight of the alkoxysilane polymer is less than 700 g/mol, the adhesion to the adhesive (DGU) may decrease, and if it exceeds 5,000 g/mol, Storage properties may be impaired.
  • the weight average molecular weight was determined by gel permeation chromatography (GPC, Gel Permeation).
  • the viscosity of the alkoxysilane polymer may be 10 to WO cPs, as measured with a Brookfield viscometer at 25 O C.
  • the viscosity of the alkoxysilane polymer is less than 10 cPs, the amount of unreacted monomer is large and thus the storage is high. It may deteriorate, and if it exceeds 100 cPs, adhesion to the body may be deteriorated.
  • the epoxy equivalent (EEW) of the alkoxysilane polymer may be 3,000 g/eq. to 5,000 g/eq..
  • EW epoxy equivalent
  • the epoxy equivalent of the alkoxysilane polymer is less than 3,000 g/eq. 2020/175860 1»(:1 ⁇ 1 ⁇ 2020/002554
  • Adhesiveness with adhesive ( 311) may be degraded, 5,000 In this case, the storability may be impaired.
  • the above epoxy equivalent can be measured according to 118 7236, or can be measured using perchloric acid, but is not limited thereto.
  • the acrylic resin contained in the primer composition of the present invention plays a role in imparting adhesiveness to the primer as well as adhesion.
  • the acrylic resin when included in the primer composition, it has particularly excellent weather resistance and gloss and color It also plays a role in improving holding power.
  • the acrylic resin may contain at least one selected from units derived from non-functional acrylate monomers.
  • the acrylic resin may further include at least one selected from units derived from a functional acrylate monomer, and the functional acrylate monomer is, for example, a glycidyl group-containing acrylate monomer and a hydroxy group-containing acrylic It may contain at least one selected from among rate monomers.
  • the acrylate monomer may include an acrylic resin obtained by reacting in a weight ratio of 5:1 to 25:1.
  • the weight ratio of the non-functional acrylate monomer and the functional acrylate monomer is less than 5:1, the weather resistance is poor. If it exceeds 25:1, the adhesive strength with the adhesive ( 311) may be poor.
  • the acrylic resin may be prepared by polymerization of one or more monomers selected from the non-functional acrylate monomers, the non-functional acrylate monomer, the glycidyl group-containing acrylate monomer and the hydroxy group-containing acrylate monomer
  • One or more monomers selected from among may be prepared by copolymerization.
  • the non-functional acrylate monomer is to impart adhesion and tackiness to the primer, specifically, alkyl (meth) acrylate,
  • the alkyl may have 1 to 1 carbon atoms
  • the cycloalkyl may have 3 to 3 carbons
  • the bicyclo Alkyl can have 5 to 20 carbon atoms.
  • the non-functional acrylate monomer is methyl methacrylate (MMA),
  • the glycidyl group-containing acrylate monomer is used in combination with a solid epoxy resin.
  • the glycidyl group of the glycidyl group-containing acrylate monomer reacts with the amino group or imino group of the silane-based monomer containing at least two amino groups or imino groups to identify the attachment site to the adhesive ( 311) (11 ⁇ :1011 £ ) (By creating -03 ⁇ 4, it can improve adhesion.
  • the glycidyl group-containing acrylate monomer is specifically
  • the hydroxy group-containing acrylate monomer is specifically
  • the functional acrylate monomer is, the glycidyl group-containing acrylate
  • the monomer and the hydroxyl group-containing acrylate monomer may be included in a weight ratio of 0.8:1 to 5:1, and may be included in a weight ratio of 1:1 to 5:1.
  • the adhesion with the adhesive 311 may be poor, and if it exceeds 5:1, the weather resistance may be poor.
  • the weight average molecular weight of the acrylic resin may be 100,000 to 200,000 11101. If the weight average molecular weight of the acrylic resin is less than 100,000 and be ⁇ 11101 has the adhesion with the adhesive carrying or 311 decrease, 200,000 can be reduced, the case where the storability / Peroni exceeded.
  • the viscosity of the acrylic resin is 25 ⁇ (: the value measured with a Brookfield viscometer is 50 to
  • the adhesion with the adhesive ( 311) may be reduced, 300 If it is exceeded, the storability may decrease.
  • the primer composition of the present invention may further include a radical polymerization initiator.
  • the radical polymerization initiator is benzoyl peroxide, tert-butyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perfivarate, tert-amylperbenzoate, tert-amylperoxyacetate, di-tert-amyl peroxide, tert-amylperoxyneodecanoate,
  • At least one selected from common polymerization initiators such as tert-butylperoxyneodecanoate, tert-amyl- (2-ethylethyl) monoperoxycarbonate, azobisisobutylnitrile, and 2.2-azobismethylbutyronitrile May include.
  • the acrylic resin may be included in an amount of 20 to 50 parts by weight based on W0 parts by weight of the alkoxysilane polymer, specifically, 25 to 45 parts by weight, more specifically, 30 to 40 parts by weight. If the content of the acrylic resin is less than 20 parts by weight based on the W0 parts by weight of the alkoxysilane polymer, there is a risk of deterioration in storage properties, and if it exceeds 50 parts by weight, the adhesion between the primer and the adhesive (DGU) may decrease. .
  • the epoxy resin contained in the primer composition of the present invention plays a role in improving the possession of the primer or adhesion to the DGU.
  • the epoxy resin may include a bisphenol-based epoxy resin, the
  • Bisphenol-based epoxy resin may specifically be a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, or a mixture thereof, but is not limited thereto. However, it is desirable to include a service phenol A type epoxy resin to secure a long house life and improve adhesion at low temperatures.
  • the epoxy resin may contain a solid epoxy resin, or a liquid
  • Epoxy resin may also be included. Solid epoxy resins such as
  • solid epoxy resins have a higher epoxy equivalent (g/eq.) than liquid epoxy resins. Since this means that the weight average molecular weight is large, the solid epoxy resin is more advantageous in film formation than the liquid epoxy resin, that is, the adhesion to the base material is better. Therefore, the solid epoxy resin in the primer composition of the present invention as above is In the case of inclusion, compared to containing the liquid epoxy resin, it is possible to secure a long housework time in the primer composition, and there is an effect of improving the adhesion at low temperatures (8 (TC or less)).
  • the epoxy equivalent of the epoxy resin may be 900 to 1,200 g/eq. If the epoxy equivalent of the solid epoxy resin is less than 900 g/eq., the adhesion to the adhesive (DGU) may be poor, and 1,200 g/eq. If it is exceeded, the weather resistance may be poor.
  • DGU adhesion to the adhesive
  • the immediate value can be 3,000 to 12,000 cPs. If the viscosity of the solid epoxy resin is less than 3,000 cPs, it may be mixed with an adhesive (DGU). The adhesion may be poor, and storage stability problems may arise if the amount exceeds 12,000 cPs.
  • DGU adhesive
  • the softening point of the solid epoxy resin (the temperature at which the solid epoxy resin melts by absorbing heat) may be 78 to 122 O C. If the softening point of the solid epoxy resin is less than 78°C, lyrics Shorter time may cause problems with storage stability, and if it exceeds 122, it may cause problems with adhesion to the adhesive (DGU).
  • the solid epoxy resin may contain two types of epoxy resins with different epoxy equivalents, and specifically, may include two types of solid epoxy resins with different epoxy equivalents.
  • epoxy equivalents may contain two different types of epoxy resins.
  • the epoxy resin of the first solid phase with a large amount and the epoxy resin of the second solid phase with a small epoxy equivalent may be included. That is, the epoxy equivalent of the epoxy resin of the first solid phase is greater than the epoxy equivalent of the epoxy resin of the second solid phase.
  • the first solid epoxy resin is a bisphenol-based epoxy resin synthesized using a fusion process, and the epoxy equivalent of the first solid epoxy resin may be 1,100 to 1,200 g/eq., and viscosity.
  • an immediate value of 5,000 to 12,000 cPs with an ICI Cone & Plate Viscometer may be 5,000 to 12,000 cPs, and the softening point may be 115 to 122° C.
  • the second solid-state epoxy resin is a bisphenol-based epoxy resin synthesized using a taffy process, and the epoxy equivalent of the second solid-phase epoxy resin may be 900 to 1,000 g/eq., and viscosity.
  • an immediate value of 3,000 to 7,000 cPs with an ICI Cone & Plate Viscometer may be,
  • the softening point can be 99 to 111 O C.
  • the epoxy equivalent of the liquid epoxy resin may be 150 to 200 g/eq..
  • the epoxy equivalent of the liquid epoxy resin is less than 150 g/eq.
  • adhesion to the adhesive (DGU) may be poor, and if it exceeds 200 g/eq., the weather resistance may be poor.
  • the viscosity of the liquid epoxy resin may be 10,000 to 15,000 cPs as measured with a Brookfield viscometer at 25 O C.
  • the viscosity of the liquid epoxy resin is less than 10,000 cPs, the adhesion with an adhesive (DGU) It may become poor, and if it exceeds 15,000 cPs, storage stability may suffer.
  • the epoxy resin may be included in an amount of 10 to 50 parts by weight based on 100 parts by weight of the alkoxysilane polymer, specifically in an amount of 10 to 30 parts by weight, and more specifically in an amount of 15 to 25 parts by weight. Can be above If the content of the epoxy resin is less than 10 parts by weight based on 100 parts by weight of the alkoxysilane polymer, adhesion at low temperatures may be deteriorated, and if it exceeds 50 parts by weight, adhesion to the adhesive (DGU) may be poor.
  • DGU adhesion to the adhesive
  • the primer composition of the present invention may further include a pigment.
  • the pigment embodies the color of the primer in the primer composition, and plays a role in making the physical properties such as weather resistance and dispersibility excellent.
  • extender pigments red series, yellow/orange series, blue series, green series, black series, white series, pearl and metallic series, etc. can be used, but are not limited thereto.
  • the pigment is, for example, barium sulfate (Ba 2 S0 4 ) (barite, barite), barite,
  • White pigments such as Lithopon, zinc sulfide, lead white (2PbCOrPb(OH) 2 ), antimony oxide (Sb 2 0 3 ); width colors such as carbon black, explosive flame, iron width (Fe 3 0 4 ) Pigments; Yellow lead (PbCr0 3 ), zinc chromate, cadmium yellow (CdS), lead cyanamide (PbCN 2 ), titanium yellow (Ti0 2 -Ni0-Sb 2 0 3 ), strontium yellow (SrCr0 4 ), etc.
  • the pigment is 10 to 30 based on 100 parts by weight of the alkoxysilane polymer
  • the content of the pigment is less than W parts by weight based on 100 parts by weight of the alkoxysilane polymer, the hiding property and appearance of the primer are lowered. If it exceeds 30 parts by weight, it may cause problems in dispersibility and storage as a primer.
  • the primer composition of the present invention may further contain a solvent.
  • the solvent may play a role of controlling the dryness of the coating film by controlling the viscosity of the primer composition.
  • the solvent may include at least one selected from the group consisting of alcohol-based solvents, ketone-based solvents, ester-based solvents and carbonate-based solvents. 2020/175860 1»(:1/10 ⁇ 020/002554
  • the alcohol-based solvent may contain methanol, ethanol, isopropanol, etc.
  • the ketone-based solvent is acetone, methyl ethyl ketone (MEK), methylpropyl ketone, methyl butyl. Ketone, ethylpropyl ketone, methyl isobutyl ketone, etc. may be included, and the ester-based solvent is methyl acetate, ethyl acetate, etc., 11-propyl acetate,
  • the carbonate-based solvent may include dimethyl carbonate (DMC).
  • DMC dimethyl carbonate
  • the solvent may contain at least one carbonate-based solvent for compatibility with the acrylic resin or the epoxy resin.
  • the solvent may be included in an amount of 50 to 300 parts by weight based on 100 parts by weight of the alkoxysilane polymer, specifically 60 to 200 parts by weight, more specifically 70 to 150 parts by weight, more preferably 70 If the content of the solvent is less than 50 parts by weight based on 100 parts by weight of the alkoxysilane polymer, the dispersibility and storage properties of the pigment may be lowered, and if the content exceeds 300 parts by weight, the base material or adhesive ( 311) The adhesion, weather resistance, etc. may be deteriorated.
  • the primer composition of the present invention may additionally contain one or more additives such as dispersants, storage stabilizers, moisture absorbers, etc. to improve the properties of the paint and film.
  • additives such as dispersants, storage stabilizers, moisture absorbers, etc.
  • the dispersing agent disperses the pigment in a uniform and stable state in the composition.
  • the grave 13 ⁇ 4 show 4061, 2063,
  • Dispersants such as ⁇ ?£1 ⁇ -2152 can be used, but this is not limited to this.
  • the above storage stabilizer prolongs the housekeeping time of the primer and saves it with workability 0561
  • Storage stabilizers may be used, but are not limited to this.
  • the moisture absorbent adjusts the moisture content of the primer composition to improve workability.
  • the moisture absorbent may include sodum/calcium aluminosilicate.
  • the additive may be included in an amount of 3 to 10 parts by weight based on 100 parts by weight of the alkoxysilane polymer.
  • amount of the additive is less than 3 parts by weight based on 100 parts by weight of the alkoxysilane polymer, the dispersibility and workability of the primer composition this may be reduced, such as storage stability, can be a reduced adhesion properties, weather resistance and so on with the adhesive 311 in the case of parts by weight is exceeded.
  • Dimethyl carbonate (DMC) and methanol were added and reacted for 20 to 25 hours at a temperature of 40°0 to 50° (:) to synthesize an alkoxysilane polymer.
  • BMA butyl methacrylate
  • GMA glycidyl methacrylate
  • a primer composition was prepared by mixing with the composition shown in Table 2 below. 2020/175860 1»(:1/10 ⁇ 020/002554
  • test piece was stored at 20° (: and humidity), and the peeling test was performed 7 days after application to observe the condition of the adhesive interface.
  • the evaluation criteria are as follows.
  • test piece was preserved at 20° (: and 65% humidity per acid), and a peeling test was conducted 7 days after application to observe the condition of the adhesive interface.
  • the evaluation criteria are as follows.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

본 발명은 아미노기 또는 이미노기를 적어도 두 개 포함하는 실란계 모노머로부터 유래되는 단위 및 트리알콕시실란계 모노머로부터 유래되는 단위를 포함하는 알콕시 실란 폴리머; 비관능성 아크릴레이트 모노머로부터 유래되는 단위 중에서 선택되는 적어도 하나를 포함하는 아크릴 수지; 및 에폭시 수지;를 포함하는 프라이머 조성물에 관한 것이다.

Description

2020/175860 1»（：1^1{2020/002554 명세서
발명의명칭:프라이머조성물
기술분야
[1] 본발명은프라이머조성물에 관한것이다.
배경기술
四 일반적으로자동차의차체와유리창과의 접착에는접착제가적용되고있지만, 접착제만을사용한접착으로는충분한접착성을얻을수없는경우가많다.이와 같이 접착제단독으로충분한접착성을얻을수없는경우에는접착면에미리 프라이머조성물을도포한후,그위에 접착제등을도포하여충분한접착성을 확보하고있다.
[3] 기존에 이용되던프라이머의주요재료로서폴리에스테르폴리우레탄이나 아크릴수지와같은바인더성분（조막성분）에실란커플링제,
폴리이소시아네이트,카본블랙등을배합한것이사용되고있었다（한국 공개특허공보제 10-2009-0066283호）.
[4] 그러나바인더성분에폴리에스테르폴리우레탄과같은우레탄수지를이용할 경우,프라이머의품질은높더라도내후성이 떨어지고,작업 공정에따른시간과 비용이 경제적이지못한문제가있었다.
[5] 특히프라이머를도포한후에 일정시간이경과하면,우레탄수지에포함된
이소시아네이트기가대기중의수분과반응하여프라이머표면의 활성이 손상되기 때문에,충분한부착성을얻기위해다시도포하는등작업성또는 재작업성이 열세한문제가있었다.또한이러한이소시아네이트기반의 자동차용프라이머는실리콘하드코팅된유리에 대해서는충분한부착성을 얻을수없는등의문제도있었다.
[6] [선행기술문헌]
[7] 한국공개특허공보제 10-2009-0066283호
발명의상세한설명
기술적과제
[8] 본발명은위와같이종래의 이소시아네이트기반의우레탄접착제용
프라이머의문제를해결하기 위한것으로서 ,저장안정성과내후성이
우수하면서도,가사시간이 길어서프라이머도포후에보관안정성 및작업성이 우수하고,특히자동차용차체뿐만아니라유리에 있어서도우수한부착성이 있는프라이머조성물을제공하고자한다.
과제해결수단
[9] 본발명은아미노기또는이미노기를적어도두개포함하는실란계
모노머로부터유래되는단위 및트리알콕시실란계모노머로부터유래되는 단위를포함하는알콕시실란폴리머;비관능성아크릴레이트모노머로부터 2020/175860 1»（：1^1{2020/002554 유래되는단위중에서선택되는적어도하나를포함하는아크릴수지;및에폭시 수지 ;를포함하는프라이머조성물을제공한다.
발명의효과
[1이 본발명의프라이머조성물은,트리알콕시실란계모노머로부터유래되는
단위와,아미노기또는이미노기를적어도두개포함하는실란계모노머로부터 유래되는단위를포함하는알콕시실란폴리머,비관능성아크릴레이트 모노머로부터유래되는단위중에서선택되는적어도하나를포함하는아크릴 수지를이용함으로써,프라이머의부착력을개선할수있으며,위와같은 프라이머조성물은저장안정성과내후성이우수하면서도,가사시간이길어서 프라이머도포후에보관안정성 및작업성이우수하고,특히자동차용차체뿐만 아니라유리에 있어서도부착성（특히,저온에서의접착성）이우수한효과가 있다.
발명의실시를위한최선의형태
[11] 이하,본발명을상세히설명하고자한다.
[12] 본발명은프라이머조성물을제공한다.
[13] 본발명의프라이머조성물은알콕시실란폴리머 ;아크릴수지 ;및에폭시
수지 ;를포함한다.
[14] ＜알콕시실란폴리머＞
[15] 본발명의프라이머조성물에포함되는알콕시실란폴리머는프라이머가소지 또는접착제 （311（0뇨 （3 : 11 1 11句）와의부착력을향상시키는역할을 한다.
[16] 상기 알콕시실란폴리머는아미노기또는이미노기를적어도두개포함하는 실란계모노머로부터유래되는단위 및트리알콕시실란계모노머로부터 유래되는단위를포함할수있다.즉,상기 알콕시실란폴리머는,상기아미노기 또는이미노기를적어도두개포함하는실란계모노머중에서선택되는하나 이상의모노머와,상기트리알콕시실란계모노머중에서선택되는하나이상의 모노머가중합또는공중합하여제조되는것일수있다.
[17] 상기트리알콕시실란계모노머는말단에트리알콕시기가치환된
트리알콕시실란계모노머일수있으며,상기트리알콕시실란계모노머는 아크릴기,메르캅토기 및글리시딜기중에서선택되는적어도한개의관능기를 포함할수있다.
[18] 상기트리알콕시실란계모노머는 3 -메타크릴로일옥시프로필트리메톡시실란, 3 -메타크릴로일옥시프로필트리에톡시실란,
3 -아크릴로일옥시프로필트리메톡시실란,
3 -아크릴로일옥시프로필트리에톡시실란, 3 -메르캅토프로필트리메톡시실란,
3 -메르캅토프로필트리에톡시실란,감마-글리시독시프로필트리메톡시실란, 감마-글리시독시프로필트리에톡시실란, 비스- (감 트리에톡시실릴프로필)아민 (bis-(gamma-Trie仕 ioxysilylpropyl)amine), 또는
비스- (감마-트리메톡시실릴프로필)아민 (bis-(gamma-Trimethoxysilylpropyl)amine) 등일수있다.
[19] 상기아미노기또는이미노기를적어도두개포함하는실란계모노머는상기 트리알콕시실란계모노머와중합반응하여알콕시실란폴리머를형성할수 있는것이면이에한정되는것은아니며 ,상기아미노기또는이미노기를적어도 두개포함하는실란계모노머는말단에트리알콕시기가치환될수있다.
[2이 상기아미노기또는이미노기를적어도두개포함하는실란계모노머가
말단에트리알콕시기가치환되는경우에는,전술한상기트리알콕시실란계 모노머와상이할수있다.
[21] 상기아미노기또는이미노기를적어도두개포함하는실란계모노머는
N- (베타-아미노에틸)-감마-아미노프로필트리메톡시실란,
N-베타- (아미노에틸)-감마-아미노프로필메틸
디메톡시실란 (N-beta-(Aminoe比 iyl)-gamma-aminopropylme比 iyl dimethoxy silane) 등을포함할수있으며,예를들어아미노기또는이미노기를적어도세개 포함하는실란계모노머 (triaminofucntional silane)를포함할수있다.
[22] 상기프라이머조성물에포함되는상기알콕시실란폴리머는,상기
트리알콕시실란계모노머와상기아미노기또는이미노기를적어도두개 포함하는실란계모노머가 1:1초과 5:1이하의중량비로반응하여얻어지는 알콕시실란폴리머를포함할수있고,예를들어 1:1초과 4:1이하의중량비로 반응하여얻어지는알콕시실란폴리머를포함할수있다.상기
트리알콕시실란계모노머와상기아미노기또는이미노기를적어도두개 포함하는실란계모노머의중량비가 1:1이하인경우에는프라이머와
접착제 (DGU)와의부착성이저하되며 , 5: 1초과인경우에는저장성이열세해질 수있다.
[23] 상기알콕시실란폴리머의중량평균분자량은 700내지 5,000 g/mol일수
있으며 ,예를들어 700내지 3,000 g/mol일수있다.상기알콕시실란폴리머의 중량평균분자량이 700 g/mol미만인경우에는접착제 (DGU)와의부착성이 저하될수있으며 , 5,000 g/mol초과인경우에는저장성이저하될수있다.
[24] 상기중량평균분자량은겔투과크로마토그래피 (GPC, Gel Permeation
Chromatography)로즉정될수있으나,이에한정되는것은아니다.
[25] 상기알콕시실란폴리머의점도는 25OC에서브룩필드점도계로측정한값이 10내지 WO cPs일수있다.상기알콕시실란폴리머의점도가 lO cPs미만인 경우에는미반응모노머의함량이많아저장성이저하될수있고, 100 cPs초과인 경우에는소지와의부착성이저하될수있다.
[26] 상기알콕시실란폴리머의에폭시당량 (EEW)은 3,000 g/eq.내지 5,000 g/eq.일 수있다.상기알콕시실란폴리머의에폭시당량이 3,000 g/eq.미만인경우에는 2020/175860 1»（：1^1{2020/002554 접착제 (311)와의부착성이저하될수있고, 5,000
Figure imgf000005_0001
경우에는 저장성이저하될수있다.
[27] 상기에폭시당량은 118 7236에따라측정할수있고,과염소산을이용하여 측정할수도있으나,이에한정되는것은아니다.
[28] ＜아크릴수지＞
[29] 본발명의프라이머조성물에포함되는아크릴수지는프라이머에부착성과 더불어점착성을부여하는역할을한다.또한,상기아크릴수지를상기 프라이머조성물에포함하는경우에는,내후성이특히우수하며광택및색상 보유력을개선하는역할도한다.
[3이 상기아크릴수지는,비관능성아크릴레이트모노머로부터유래되는단위 중에서선택되는적어도하나를포함할수있다.
[31] 상기아크릴수지는,관능성아크릴레이트모노머로부터유래되는단위중에서 선택되는적어도하나를더포함할수있으며,관능성아크릴레이트모노머는, 예를들어,글리시딜기함유아크릴레이트모노머및히드록시기함유 아크릴레이트모노머중에서선택되는적어도하나를포함할수있다.
[32] 상기아크릴수지는,상기비관능성아크릴레이트모노머와상기관능성
아크릴레이트모노머가 5:1내지 25:1의중량비로반응하여얻어지는아크릴 수지를포함할수있다.상기비관능성아크릴레이트모노머와상기관능성 아크릴레이트모노머의중량비가 5:1미만인경우에는내후성이불량해질수 있고, 25:1초과인경우에는접착제必(311)와의부착력이불량해질수있다.
[33] 즉상기아크릴수지는,상기비관능성아크릴레이트모노머중에서선택되는 하나이상의모노머가중합하여제조될수있고,상기비관능성아크릴레이트 모노머와,상기글리시딜기함유아크릴레이트모노머및상기히드록시기함유 아크릴레이트모노머중에서선택되는하나이상의모노머가공중합하여 제조되는것일수있다.
[34] 상기비관능성아크릴레이트모노머는특히프라이머에부착성및점착성을 부여하는것으로서,구체적으로알킬 (메트)아크릴레이트,
시클로알킬 (메트)아크릴레이트및비시클로알킬 (메트)아크릴레이트로 이루어진군에서선택되는하나이상일수있다.이때상기알킬은탄소수 1 내지 일수있고,상기시클로알킬은탄소수 3내지 일수있으며,상기 비시클로알킬은탄소수 5내지 20일수있다.
[35] 상기비관능성아크릴레이트모노머는메틸메타크릴레이트 (MMA),
에틸메타크릴레이트,부틸메타크릴레이트 (BMA),이소부틸메타크릴레이트, 터셔리부틸메타크릴레이트,노말핵실메타크릴에이트,
2 -에틸핵실메타크릴레이트,이소보닐메타크릴레이트,
시클로핵실메타크릴레이트,메틸아크릴레이트,에틸아크릴레이트,
프로필아크릴레이트,노말부틸아크릴레이트,이소부틸아크릴레이트, 터셔리부틸아크릴레이트, 2 -에틸핵실아크릴레이트,노말옥틸아크릴에이트, 2020/175860 1»（：1^1{2020/002554 또는시클로핵실아크릴레이트등일수있으나,이에한정되는것은아니다.
[36] 상기글리시딜기함유아크릴레이트모노머는고상의에폭시수지와의
상용성을높여주고,접착제 (311)와의부착성을높여주는역할을한다.
구체적으로상기글리시딜기함유아크릴레이트모노머의글리시딜기가상기 아미노기또는이미노기를적어도두개포함하는실란계모노머의아미노기 또는이미노기와반응하여접착제 (311)와의부착부위知(11^:1011 £)(-0¾를 생성하여부착성을향상시킬수있다.
[37] 상기글리시딜기함유아크릴레이트모노머는구체적으로
글리시딜메타크릴
Figure imgf000006_0001
-에폭시시클로핵실메타크릴레이트,
Figure imgf000006_0002
아니다.
[38] 상기히드록시기함유아크릴레이트모노머는접착제 (311)와의부착
부위 (-0¾를형성할수있어서,특히프라이머에내후성을개선하는역할을 한다.
[39] 상기히드록시기함유아크릴레이트모노머는구체적으로
2 -히드록시에틸메타크릴레이트,히드록시에틸메타크릴레이트,
2 -히드록시프로필메타아크릴레이트, 2 -히드록시에틸아크릴레이트,
2 -히드록시프로필아크릴레이트, 2, 3 -디히드록시프로필아크릴레이트,
2, 3 -디히드록시프로필메타크릴레이트,
4 -히드록시메틸시클로핵실-메틸메타크릴레이트,또는
2 -히드록시- 3 -페녹시프로
Figure imgf000006_0003
있으나,이에한정되는 것은아니다.
[4이 상기관능성아크릴레이트모노머는,상기글리시딜기함유아크릴레이트
모노머및상기히드록시기함유아크릴레이트모노머를 0.8:1내지 5:1의 중량비로포함할수있고, 1:1내지 5:1의중량비로포함할수있다.상기
글리시딜기함유아크릴레이트모노머와상기히드록시기함유아크릴레이트 모노머의중량비가 0.8:1미만인경우에는접착제 (311)와의부착력이불량해질 수있고, 5:1초과인경우에는내후성이불량해질수있다.
[41] 상기아크릴수지의중량평균분자량은 100,000내지 200,000 11101일수있다. 상기아크릴수지의중량평균분자량이 100,000 ^11101미만인경우에는소지또는 접착제 (311)와의부착성이저하될수있고, 200,000은/뻬초과인경우에는 저장성이저하될수있다.
[42] 상기아크릴수지의점도는 25ᄋ(：에서브룩필드점도계로측정한값이 50내지
300。모8일수있다.상기아크릴
Figure imgf000006_0004
접착제 (311)와의부착성이저하될수있고, 300
Figure imgf000006_0005
초과인경우에는저장성이 저하될수있다.
[43] 상기아크릴수지의중합을위해서본발명의프라이머조성물은라디칼중합 개시제를더포함할수있다.상기라디칼중합개시제는벤조일퍼옥사이드, tert-부틸퍼옥사이드, di-tert-부틸퍼옥사이드, tert-부틸퍼벤조에이트, tert-부틸퍼피바레이트, tert-아밀퍼벤조에이트, tert-아밀퍼옥시아세테이트, di-tert-아밀퍼옥사이드, tert-아밀퍼옥시네오데카노에이트,
tert-부틸퍼옥시네오데카노에이트, tert-아밀- (2 -에틸에실)모노퍼옥시카보네이트, 아조비스이소부틸니트릴, 2.2 -아조비스메틸부티로니트릴등의일반적인중합 개시제중에서선택되는적어도한개를포함할수있다.
[44] 상기아크릴수지는상기알콕시실란폴리머 W0중량부를기준으로 20내지 50중량부의함량으로포함될수있고,구체적으로는 25내지 45중량부의함량, 더구체적으로는 30내지 40중량부의함량으로포함될수있다.상기아크릴 수지의함량이상기알콕시실란폴리머 W0중량부를기준으로 20중량부 미만인경우에는저장성이저하될우려가있고, 50중량부초과인경우에는 프라이머와접착제 (DGU)와의부착성이저하될수있다.
[45] ＜에폭시수지＞
[46] 본발명의프라이머조성물에포함되는에폭시수지는프라이머의소지또는 DGU와의부착성을향상시키는역할을한다.
[47] 상기에폭시수지는비스페놀계에폭시수지를포함할수있으며 ,상기
비스페놀계에폭시수지는구체적으로비스페놀 A형에폭시수지,비스페놀 F형 에폭시수지,또는이들의혼합물등일수있으나,이에한정되는것은아니다. 다만,긴가사시간을확보하고저온에서의부착성개선을위해서비스페놀 A형 에폭시수지를포함하는것이바람직하다.
[48] 상기에폭시수지는고상의에폭시수지를포함할수도있고,또는액상의
에폭시수지를포함할수도있다.위와같은고상의에폭시수지는필름
형성 (Film formation)역할을하고,접착제 (DGU)와의부착성을부여하는역할을 할수있다.특히,고상의에폭시수지는액상의에폭시수지에비하여에폭시 당량 (g/eq.)이크다.에폭시당량이크다는것은중량평균분자량이크다는것을 의미하므로,고상의에폭시수지일수록액상의에폭시수지에비하여필름 형성에유리 ,즉소지와의부착력이우수하게된다.따라서 ,위와같이본발명의 프라이머조성물에고상의에폭시수지를포함하는경우에는,액상의에폭시 수지를포함하는것에비하여,프라이머조성물에긴가사시간을확보할수 있으며,저온 (8(TC이하)에서의부착성을개선할수있는효과가있다.
[49] 상기에폭시수지가고상의에폭시수지를포함하는경우에는,상기고상의
에폭시수지의에폭시당량은 900내지 1,200 g/eq.일수있다.상기고상의 에폭시수지의에폭시당량이 900 g/eq.미만인경우에는접착제 (DGU)와의 부착성이불량해질수있고, 1,200 g/eq.초과인경우에는내후성이불량해질수 있다.
[5이 상기고상의에폭시수지의점도는 150OC에서 I.C.I콘플레이트점도계 (I.C.I
Cone & Plate Viscometer)로즉정한값이 3,000내지 12,000 cPs일수있다.상기 고상의에폭시수지의점도가 3,000 cPs미만인경우에는접착제 (DGU)와의 부착성이불량해질수있고, 12,000 cPs초과인경우에는저장안정성에문제가 생길수있다.
[51] 상기고상의에폭시수지의연화점 (softening point:고상의에폭시수지가열을 흡수하여서녹아내리는온도)은 78내지 122OC일수있다.상기고상의에폭시 수지의연화점이 78°C미만인경우에는가사시간이짧아져서저장안정성에 문제가생길수있고, 122 초과인경우에는접착제 (DGU)와의부착성에문제가 생길수있다.
[52] 또한상기고상의에폭시수지는에폭시당량이서로다른 2종의에폭시수지를 포함할수있고,구체적으로는에폭시당량이서로다른 2종의고상의에폭시 수지를포함할수있다.예를들어에폭시당량이큰제 1고상의에폭시수지와, 에폭시당량이작은제 2고상의에폭시수지를포함할수있다.즉,상기제 1 고상의에폭시수지의에폭시당량은,상기제 2고상의에폭시수지의에폭시 당량보다큰값을가질수있다.
[53] 위와같이상기에폭시수지로,에폭시당량이상대적으로큰제 1고상의
에폭시수지와,에폭시당량이상대적으로작은제 2고상의에폭시수지를 혼용하는경우에는저온에서의소지또는접착제 (DGU)와의부착성을개선시킬 수있다.
[54] 상기제 1고상의에폭시수지는퓨전공정 (Fusion process)을이용하여합성한 비스페놀계에폭시수지로서,상기제 1고상의에폭시수지의에폭시당량은 1,100내지 1,200 g/eq.일수있고,점도는 150OC에서 I.C.I콘플레이트점도계 (I.C.I Cone & Plate Viscometer)로즉정한값이 5,000내지 12,000 cPs일수있으며 , 연화점 (softening point)은 115내지 122°C일수있다.
[55] 상기제 2고상의에폭시수지는태피공정 (Taffy process)을이용하여합성한 비스페놀계에폭시수지로서,상기제 2고상의에폭시수지의에폭시당량은 900 내지 1,000 g/eq.일수있고,점도는 150OC에서 I.C.I콘플레이트점도계 (I.C.I Cone & Plate Viscometer)로즉정한값이 3,000내지 7,000 cPs일수있으며 ,
연화점 (softening point)은 99내지 111OC일수있다.
[56] 상기에폭시수지가액상의에폭시수지를포함하는경우에는,상기 액상의 에폭시수지의에폭시당량은 150내지 200 g/eq.일수있다.상기 액상의에폭시 수지의에폭시당량이 150 g/eq.미만인경우에는접착제 (DGU)와의부착성이 불량해질수있고, 200 g/eq.초과인경우에는내후성이불량해질수있다.
[57] 상기액상의에폭시수지의점도는 25OC에서브룩필드점도계로측정한값이 10,000내지 15,000 cPs일수있다.상기 액상의에폭시수지의점도가 10,000 cPs 미만인경우에는접착제 (DGU)와의부착성이불량해질수있고, 15,000 cPs 초과인경우에는저장안정성에문제가생길수있다.
[58] 상기에폭시수지는상기알콕시실란폴리머 100중량부를기준으로 10내지 50중량부의함량으로포함될수있고,구체적으로는 10내지 30중량부의 함량으로,더구체적으로는 15내지 25중량부의함량으로포함될수있다.상기 에폭시수지의함량이상기알콕시실란폴리머 100중량부를기준으로 10 중량부미만인경우에는저온에서의부착성이저하될수있으며 , 50중량부 초과인경우에는접착제 (DGU)와의부착성이불량해질수있다.
[59] ＜안료＞
[6이 본발명의프라이머조성물은안료를더포함할수있다.상기안료는프라이머 조성물에서프라이머의색상을구현하며,내후성,분산성등의물성을우수하게 하는역할을한다.
[61] 상기안료로는체질안료,레드계열,황색/오렌지계열,블루계열,녹색계열, 블랙계열,백색계열,펄및메탈릭계열등을사용할수있으나,이에한정되는 것은아니다.
[62] 상기안료는예를들어 ,황산바륨 (Ba2S04)(바라이트, barite),중정석 ,
탄산칼슘 (CaC03),클레이 (점토, Al203-2Si02-2H20),골석분 (3MgO.4SiO2.H20), 규석분 (Si02),규조토 (Si02.nH20),실리카,벤토나이트,탈크 (Talc),알루미늄 실리케이트등의체질안료;산화티탄 (예, Ti02),산화아연 (ZnO),
리토폰 (Lithopon),황화아연,연백 (2PbCOrPb(OH)2),산화안티몬 (Sb203)등의백색 안료;카본블랙 (carbon black),폭연,철폭 (Fe304)등의폭색안료;황연 (PbCr03), 징크크로메이트 (Zinc chromate),카드뮴옐로 (CdS),리드시안아미드 (PbCN2), 티타늄옐로 (Ti02-Ni0-Sb203),스트론튬옐로 (SrCr04)등의황색안료;철적 (Fe203 ),연단 (Pb304),은주 (HgS),카드뮴레드 (CdS와 HgS와의혼합결정),몰리브덴 레드 (PbCr04와 PbMo04, PbS04의혼합결정),아산화동 (Cu20)등의적색안료; 감청 (MFe[Fe(CN)6], M=K, NH4, Na),군청 (2(Al2Na2Si301()).Na2S4),코발트 블루 (Co0.nAl203)등의청색안료;크롬녹 (PbCr04과감청 KFe[Fe(CN)6]의 혼합물),산화크롬 (Cr203),수산화크롬 (Cr20r2H20)등의녹색안료;
은분 (Alluminium powder),금분 (Bronze powder)등의금속분말안료;및천연펄 에센스,합성펄안료등의펄안료로이루어진군에서선택되는적어도하나일 수있으나,이에한정되는것은아니며,본발명의프라이머조성물의색상및 내후성을향상시키기위해카본블랙을이용하는것이바람직하다.
[63] 상기안료는상기알콕시실란폴리머 100중량부를기준으로 10내지 30
중량부의함량으로포함될수있고,더구체적으로는 15내지 20중량부의 함량으로포함될수있다.상기안료의함량이상기알콕시실란폴리머 100 중량부를기준으로 W중량부미만인경우에는프라이머의은폐성및외관이 저하될수있으며 , 30중량부초과인경우에는프라이머로서분산성및저장성에 문제가발생할수있다.
[64] ＜용제＞
[65] 본발명의프라이머조성물은용제를더포함할수있다.상기용제는프라이머 조성물의점도를조절하여도막의건조성을조절하는역할을할수있다.
[66] 상기용제는알코올계용제，케톤계용제 ,에스테르계용제및카르보네이트계 용제로이루어진군에서선택되는적어도한개를포함할수있다. 2020/175860 1»（：1/10公020/002554 상기 알코올계용제는메탄올,에탄올,이소프로판올등을포함할수있고,상기 케톤계용제는아세톤,메틸에틸케톤 (MEK),메틸프로필케톤,메틸부틸케톤, 에틸프로필케톤,메틸이소부틸케톤등을포함할수있고,상기 에스테르계 용제는메틸아세테이트,에틸아세테이트田쇼), 11-프로필아세테이트,
11-부틸아세테이트,에틸에톡시프로피오네이트등을포함할수있고,상기 카르보네이트계용제는디메틸카르보네이트 (DMC)등을포함할수있다.
[68] 상기용제는상기아크릴수지또는상기 에폭시수지와의상용성을위해서 카르보네이트계용제를적어도한개포함할수있다.
[69] 상기용제는상기 알콕시실란폴리머 100중량부를기준으로 50내지 300 중량부의 함량으로포함될수있고,구체적으로는 60내지 200중량부,더 구체적으로는 70내지 150중량부,더 바람직하게는 70내지 120중량부의 함량으로포함될수있다.상기용제의 함량이상기 알콕시실란폴리머 100 중량부기준으로 50중량부미만인경우에는안료의분산성 ,저장성이 저하될수 있고, 300중량부초과인경우에는소지또는접착제 (311)와의부착성 ,내후성 등이 저하될수있다.
<그외첨가제 >
본발명의프라이머조성물은도료및도막의물성을향상시키기위해분산제, 저장안정제 ,수분흡수제등과같은하나이상의 첨가제를추가로포함할수 있다.
[72] 상기분산제는안료를조성물내에서균일하고안정한상태로분산시키는
역할을하는것으로서 ,묘1¾쇼 4061, 2063,
Figure imgf000010_0001
1)犯?£1出¥ -2152등의분산제를이용할수있으나,이에 한정되는것은아니다.
]] ]] 상기 저장안정제는프라이머의가사시간을길게하여 작업성과함께 저장 0561
7777 67 73 안정성을부여하는역할을하는것으로서，디에틸말로네이트등의
저장안정제를이용할수있으나,이에 한정되는것은아니다.
[74] 상기수분흡수제는프라이머조성물의수분함량을조절하여작업성을
향상시키는역할을한다.
상기수분흡수제는소둠/칼슘알루미노실리케이트등을포함할수있다.
상기 첨가제는상기 알콕시실란폴리머 100중량부를기준으로 3내지 10 중량부의 함량으로포함될수있다.상기 첨가제의함량이상기 알콕시실란 폴리머 100중량부기준으로 3중량부미만인경우에는프라이머조성물의 분산성,작업성,저장안정성등이 저하될수있으며, 중량부초과인경우에는 접착제 (311)와의부착성,내후성등이 저하될수있다.
[77] 이하,실시예를통해본발명을보다구체적으로설명한다.그러나이들
실시예는본발명의 이해를돕기 위한것일뿐어떠한의미로든본발명의 범위가이들실시예로한정되는것은아니다.
8] 2020/175860 1»（：1^1{2020/002554 9] ＜제조예＞
[8이 ＜제조예 1＞ -알콕시실란폴리머의합성
[81] 반응용기에
감마-글리시독시프로필트리메톡시실란 (0&111111&-(}1) (1(«)中]'(¾))4 11161；11(«) 1&116 틸)-감마-아미노프로필-트리메톡시실란 -05 -&111111061；11)4)-은&
Figure imgf000011_0001
11161；11(«) 1 6),용제로서메틸에틸케톤 (1 £1(),
디메틸카르보네이트 (DMC),메탄올을넣고 40°0 ~ 50ᄋ (:의온도에서 20 ~ 25시간 반응시켜알콕시실란폴리머를합성하였다.
[82] 이때용제의양은반응물총중량의 80중량%를넘지않게조절하였고,알콕시 실란폴리머의에폭시당량田£\¥)는 3,000내지 5,000
Figure imgf000011_0002
었다.
[83] 상기제조예 1에서각성분의함량은하기표 1에나타내었다.
[84] ＜제조예 2＞ -아크릴수지의합성
[85] 메틸에틸케톤 (MEK)에메틸메타크릴레이트 (MMA),
부틸메타크릴레이트 (BMA),글리시딜메타크릴레이트 (GMA),
2 -하이드록시 -3 -페녹시프로필아
Figure imgf000011_0003
부틸퍼옥사이드 0^1)0)를혼합한후, 75°0 ~ 85ᄋ(：에서 10 ~ 15시간동안 라디칼중합반응시켜아크릴수지를합성하였다.
[86] 상기제조예 2에서각성분의함량은하기표 1에나타내었다.
[87]
[88] ＜실시예＞
[89] ＜실시예 1내지 8＞
[9이 하기표 1에나타낸조성으로배합하여고속교반기를이용하여약 400내지
800 이으로 40분간프리믹싱 (]고6111뇨11¾)하였다.프리믹싱이끝나면분산기 1¾ 血11)를이용하여약 400내지 800 111으로 70내지 100분간분산시켰다.이때 내부온도를 30ᄋ (:가넘지않게유지하였고,최종입도가 10 ^이하가될때까지 분산시켜,프라이머조성물을제조하였다.
[91]
2020/175860 1»(：1/10公020/002554
[92] [표 1]
Figure imgf000012_0001
2020/175860 1»（：1/10公020/002554
Figure imgf000013_0001
[93] <비교예 1내지 5>
[94] 하기표 2에나타낸조성으로배합하여프라이머조성물을제조하였다. 2020/175860 1»(：1/10公020/002554
[95] [표 2]
Figure imgf000014_0001
WO 2020/175860 1»（：1^1{2020/002554
Figure imgf000015_0001
[96] <실험예 >
[97] 상기실시예 1내지 8및비교예 1내지 5에서얻어진프라이머조성물및
프라이머의물성을다음과같은방법으로측정한결과를하기표 3및표 4에 나타내었다.
[98] 1）내후성평가
[99] 내후성평가방법은 XENON WEATHER-O-METER（WOM）에서 1 ,000시간
시편을폭로하고,폭로후외관상태를육안으로확인한다.
[10이 （XENON시험조건은 MS600-35에따른다）
[101] ◦（우수）: WOM폭로후외관이흑색인것
[102] A（양호）: WOM폭로후외관이흑색에가까운것
[103] X（불량）: WOM폭로후외관이백색에가까운것
[104] 2）침강성평가
[105] 카본블랙의침강성을육안으로관찰하여평가한다.평가기준은다음과같다.
[106] ◦（우수）: 20OC에서 1주간정치한후의상등액의도포막이흑색인것
[107] A（양호）: 20OC에서 1주간정치한후의상등액의도포막이흑색에가까운것
[108] X（불량）: 20OC에서 1주간정치한후의상등액의도포막이흑색이아닌것 [109] 3）부착성평가
[110] 유리또는유리표면에실리콘경질피복된피착체에조제된하도제조성물을 도포면적 25내지 150 111111로하여도포하고,그위에우레탄밀봉제와 접착제 [^0,상품명 :：?119370-：81幻를압착시켜시험편으로하였다.
[111] 시험편은 20ᄋ（:및습도 에서보존하고,도포후 7일이경과한때에박리 시험을실시하여접착계면의상태를관찰하였다.평가기준은다음과같다.
[112] ◦（우수）:밀봉제층의응집파괴 90%초과
[113] 스（양호）:밀봉제층의응집파괴 30%이상 90%이하
[114] 자불량）:밀봉제-하도제계면이 파괴,밀봉제층의응집파괴 30%미만
[115] 4）가사부착성 평가
[116] 유리또는유리표면에실리콘경질피복된피착체에조제된하도제조성물을 도포면적 25내지 150 111111로하여도포하고,그시험편은 20°0및습도 65%1 1 조건에서 3개월방치후그위에우레탄밀봉제와접착제限 그,상품명:
15119370-：81幻를압착시켜시험편으로하였다.
[117] 시험편은 20ᄋ（:및습도 65%1산1에서보존하고,도포후 7일이경과한때에박리 시험을실시하여접착계면의상태를관찰하였다.평가기준은다음과같다.
[118] ◦（우수）:밀봉제층의응집파괴 90%초과
[119] 스（양호）:밀봉제층의응집파괴 30%이상 90%이하
[12이 자불량）:밀봉제-하도제계면이 파괴,밀봉제층의응집파괴 30%미만
[121] 5）저장안정성 평가
[122] 배합후 60ᄋ（：에서 일간저장한하도제조성물을평가하였다.평가기준은 다음과같다.
[123] ◦（우수）:바닥에침전물이 5%이하이고,겔화가없는상태
[124] 스（양호）:바닥에침전물이 5%초과 10%미만이고,겔화가없는상태
[125] （불량）:겔화가생기거나바닥에침전물이 10%이상인상태
[126] [표 3]
2020/175860 1»(：1/10公020/002554
[127] [표 4]
Figure imgf000017_0001
[128]

Claims

2020/175860 1»（：1/10公020/002554 청구범위
[청구항 1] 아미노기또는이미노기를적어도두개포함하는실란계모노머로부터 유래되는단위및트리알콕시실란계모노머로부터유래되는단위를 포함하는알콕시실란폴리머 ;
비관능성아크릴레이트모노머로부터유래되는단위중에서선택되는 적어도하나를포함하는아크릴수지 ;및
에폭시수지;
를포함하는프라이머조성물.
[청구항 2] 청구항 1에있어서,
상기알콕시실란폴리머는,상기트리알콕시실란계모노머와상기 아미노기또는이미노기를적어도두개포함하는실란계모노머가 1:1 초과 5:1이하의중량비로반응하여얻어지는알콕시실란폴리머를 포함하는프라이머조성물.
[청구항 3] 청구항 1에있어서,
상기아크릴수지는관능성아크릴레이트모노머로부터유래되는단위를 더포함하고,
상기관능성아크릴레이트모노머는글리시딜기함유아크릴레이트 모노머및히드록시기함유아크릴레이트모노머중에서선택되는 적어도하나를포함하는프라이머조성물.
[청구항 4] 청구항 3에있어서,
상기아크릴수지는상기비관능성아크릴레이트모노머와상기관능성 아크릴레이트모노머를 5:1내지 25:1의중량비로반응하여얻어지는 아크릴수지를포함하는프라이머조성물.
[청구항 5] 청구항 1에있어서,
상기에폭시수지는비스페놀계에폭시수지를포함하는프라이머 조성물.
[청구항 6] 청구항 1에있어서,
상기에폭시수지는상기알콕시실란폴리머 100중량부기준으로 10 내지 50중량부의함량으로포함되는프라이머조성물.
[청구항 7] 청구항 1에있어서,
안료,용제,수분톱수제,분산제및저장안정제로이루어진군에서 선택되는적어도하나를더포함하는프라이머조성물.
PCT/KR2020/002554 2019-02-25 2020-02-21 프라이머 조성물 Ceased WO2020175860A1 (ko)

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KR20200103443A (ko) 2020-09-02
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EP3933004A4 (en) 2022-04-20
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