WO2018179178A1 - 二液硬化型ウレタン系組成物 - Google Patents
二液硬化型ウレタン系組成物 Download PDFInfo
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- WO2018179178A1 WO2018179178A1 PCT/JP2017/013059 JP2017013059W WO2018179178A1 WO 2018179178 A1 WO2018179178 A1 WO 2018179178A1 JP 2017013059 W JP2017013059 W JP 2017013059W WO 2018179178 A1 WO2018179178 A1 WO 2018179178A1
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- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- C08G18/78—Nitrogen
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Definitions
- the present disclosure relates to a two-component curable urethane composition.
- Steel plates are generally used for interior and exterior parts of automobile bodies, front doors, rear doors, back doors, front bumpers, rear bumpers, rocker moldings, etc., but weight reduction is required to meet recent demands for improving fuel economy. It has been. For this reason, the case where plastic materials, such as a polypropylene, are used as an interior / exterior part of a motor vehicle instead of a steel plate is increasing. In addition, since plastic materials, such as a polypropylene, have low intensity
- Urethane compositions have been proposed as adhesives between plastic automotive parts such as polypropylene.
- Known urethane-based compositions include a one-component composition called a moisture-curable composition that is cured by moisture in the air and the like, and a two-component composition comprising a main agent and a curing agent.
- pot life pot life, time until the paint starts to harden due to a chemical reaction or the like in a multi-component paint
- Liquid type is preferred.
- a polypropylene base material has a small surface polarity and is difficult to adhere
- surface treatment for introducing a polar group to the surface of the base material is performed in order to facilitate adhesion.
- Plasma treatment, corona treatment, flame treatment, etc. are applied to the surface treatment.
- the urethane composition is applied after pretreatment of each polypropylene substrate as a pretreatment. It is common to do.
- non-primer treatment has been demanded in the adhesion of urethane-based compositions from the viewpoint of process simplification and work environment improvement.
- the elimination (lessness) of the primer treatment process is a significant requirement in the automobile manufacturing process, where the tact management of the assembly process is severe.
- Patent Document 1 discloses a one-part moisture-curing non-primer adhesive (urethane composition).
- the non-primer adhesive of Patent Document 1 is a one-component type, there is a concern that foaming during the curing process or deep part curability is poor.
- hardenability judges the hardening condition inside the film which does not contact the water
- the mixing ratio of the main agent and the curing agent is often limited to 1: 1, but from the viewpoint of improving the adhesive strength, it is excellent when the amount of the main agent is increased. It is desirable to demonstrate the performance.
- the present disclosure provides a two-component urethane composition that is excellent in deep part curability, fast curability and non-primer adhesiveness when the mixing mass ratio of the main agent and the curing agent is in the range of 3: 1 to 10: 1.
- the purpose is to provide.
- the main agent (A) contains a urethane prepolymer (a), a polyisocyanate compound isocyanurate-modified product (b) and a silane coupling agent (c), and a content of the polyisocyanate compound isocyanurate-modified product (b).
- the curing agent (B) contains a polyol (d) having a hydroxyl value of 50 to 500 mg KOH / g and an amine catalyst (e), and the content of the polyol (d) is 40 with respect to the total amount of the curing agent (B).
- the content of the amine catalyst (e) is 1.0-10.0 mass% with respect to the total amount of the curing agent (B)
- the mixing mass ratio of the main agent (A) and the curing agent (B) is 3: 1 to 10: 1, and the NCO / OH group equivalent ratio in the main agent (A) and the curing agent (B) is 1.0 to 5
- a two-component curable urethane composition which is 0.0.
- At least one of the main agent (A) and the curing agent (B) further contains carbon black (f), and the total content of the carbon black (f) is equal to the total amount of the main agent (A) and the curing agent (B).
- At least one of the main agent (A) and the curing agent (B) further contains kaolin clay (g), and the total content of the kaolin clay (g) is equal to the total amount of the main agent (A) and the curing agent (B).
- urethane prepolymer (a) is a reaction product of a polyether polyol (a-1) having a number average molecular weight of 8000 or more and diphenylmethane diisocyanate (a-2)
- a-1 polyether polyol having a number average molecular weight of 8000 or more
- diphenylmethane diisocyanate (a-2) The two-component curable urethane composition as described in 1.
- the mixing mass ratio of the main agent and the curing agent is in the range of 3: 1 to 10: 1, the deep curable property, the fast curable property, and the non-primer adhesive property. Excellent.
- the two-component curable urethane composition of the present embodiment (hereinafter also simply referred to as “urethane composition”) includes a main agent (A) and a curing agent (B).
- This urethane composition can be cured by mixing the main agent (A) and the curing agent (B).
- mixing is performed so that the mass ratio of the main agent (A) and the curing agent (B) is 3: 1 to 10: 1.
- the main agent (A) contains a urethane prepolymer (a), a polyisocyanate compound isocyanurate-modified product (b), and a silane coupling agent (c).
- the curing agent (B) contains a polyol (d) having a hydroxyl value of 50 to 500 mg KOH / g and an amine catalyst (e).
- At least one of the main agent (A) and the curing agent (B) preferably contains at least one of carbon black (f), kaolin clay (g), and plasticizer (h).
- the urethane prepolymer (a) is a reaction product of a compound having two or more active hydrogen groups and a polyisocyanate compound having two or more isocyanate groups.
- the urethane prepolymer of the present embodiment is preferably one having an isocyanate group in the molecule by reacting so that the number of isocyanate groups becomes excessive.
- the active hydrogen group include a hydroxy group (OH group), a carboxyl group (COOH group), an amino group (NH 2 group), and a thiol group (SH group).
- the compound having two or more active hydrogen groups is preferably a polyol, more preferably a polyether polyol (a-1).
- polyisocyanate compound examples include aromatic polyisocyanates in which isocyanate groups are bonded to aromatic hydrocarbons, and alicyclic polyisocyanates in which isocyanate groups are bonded to alicyclic hydrocarbons.
- aromatic polyisocyanates are preferred, diphenylmethane diisocyanate (a-2) or dicyclohexylmethane diisocyanate (H 12 MDI) is more preferred, and diphenylmethane diisocyanate (a-2) is even more preferred.
- a compound having two or more active hydrogen groups and a polyisocyanate compound having two or more isocyanate groups may be used alone or in combination of two or more.
- the polyether polyol (a-1) is not particularly limited as long as it is a polyether polyol having two or more OH groups. Specific examples include polyethylene glycol (PEG), polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and sorbitol-based polyol. Among these, polypropylene glycol (PPG) is preferable.
- the polyether polyol (a-1) may be used alone or in combination of two or more.
- the polyether polyol (a-1) preferably has a number average molecular weight of 8000 or more, and more preferably a number average molecular weight of 10,000 or more.
- the cohesive force of the prepolymer when urethane is formed does not become too large, so that an adhesive having excellent heat-resistant creep resistance is obtained.
- Polyether polyol can be increased in molecular weight by reducing the amount of by-products generated during the production process and making it more narrowly dispersed.
- the highest number average molecular weight of PPG (polypropylene glycol) currently on the market is about 15000.
- Preminol 3012 used in the examples is a polymer of polypropylene glycol using glycerin as an initiator.
- number average molecular weight is calculated using a standard polystyrene calibration curve using gel permeation chromatography (GPC). The GPC measurement conditions are as follows.
- Measurement equipment ACQUITY UPLC APC system (manufactured by Waters) Column: APC XT-900, APC XT-200, APC XT-125, APC XT-45 (manufactured by Waters) ⁇ Carrier: Tetrahydrofuran (THF) -Detector: Differential refraction-Sample: 0.5 mass% THF solution-Calibration curve: Polystyrene
- the isocyanurate-modified product (b) of the above polyisocyanate compound includes various polydiisocyanates such as toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), naphthalene diisocyanate (NDI), and isophorone diisocyanate (IPDI).
- the trimer may be a trimer of one kind of polyisocyanate compound or may be a mixed trimer of two or more kinds of polyisocyanate compounds, for example, HDI and TDI. All of the trifunctional terminal functional groups of the trimer are isocyanate groups (NCO groups).
- polyisocyanate compound isocyanurate-modified product (b) examples include, for example, TDI isocyanurate trimer (Takenate D204, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.), HDI isocyanurate trimer (Sumidule N3300, Residential). Chemicalized Bayer Urethane Co., Ltd.), IPDI isocyanurate trimer (T1890, manufactured by Evonik Japan Co., Ltd.), mixed isocyanurate trimer of HDI and TDI (Desmodur HL, manufactured by Sumika Bayer Urethane Co., Ltd.), etc. Commercial products can be used.
- the isocyanurate modified body (b) of the polyisocyanate compound may be used alone or in combination of two or more.
- non-primer adhesion and wet heat aging resistance can be improved.
- the reason why the non-primer adhesion can be improved is that three isocyanate groups (—NCO) present in the molecule of the isocyanurate-modified polyisocyanate compound form a urethane bond in the urethane-based composition.
- —NCO isocyanate groups
- the content of the polyisocyanate compound isocyanurate-modified (b) in the urethane-based composition is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the urethane prepolymer (a), and 1.0 to 2 It is preferably 5 parts by mass.
- the content of the isocyanurate-modified product (b) of the polyisocyanate compound is less than 0.5 parts by mass, the amount of isocyanurate rings in the urethane-based composition decreases, resulting in a decrease in cohesive force. Aging is deteriorated.
- the content of the isocyanurate-modified product (b) of the polyisocyanate compound exceeds 3.0 parts by mass, the amount of NCO groups in the urethane composition increases, and as a result, the urethane composition is cured. In this case, the degree of curing becomes high, and stress may concentrate on the interface of the base material at the time of peeling, which may cause interface destruction, that is, adhesiveness is deteriorated.
- the silane coupling agent (c) is an organosilicon compound having two types of functional groups having different reactivity in one molecule.
- Examples of the silane coupling agent (c) include epoxy silane, vinyl silane, imidazole silane, mercapto silane, amino silane, styryl silane, isocyanate silane, sulfide silane, ureido silane, and the like.
- mercaptosilane, aminosilane, sulfide silane, and isocyanate silane are suitable.
- the silane coupling agent (c) forms a urethane bond and a siloxane bond in the urethane-based composition, and forms a covalent bond with the polar group introduced by subjecting the polypropylene substrate surface to a flame treatment as a partner. Form. For this reason, it contributes to adhesion
- These silane coupling agents may be used alone or in combination of two or more.
- the content of the silane coupling agent (c) is 0.5 to 5.0 parts by mass, preferably 1.0 to 4.0 parts by mass with respect to 100 parts by mass of the urethane prepolymer (a). More preferably, it is 1.5 to 2.5 parts by mass.
- the content of the silane coupling agent (c) is less than 0.5 parts by mass, the adhesion between the urethane-based composition and the polypropylene substrate is reduced, and as a result, non-primer adhesion particularly at high temperatures is achieved. Get smaller.
- a silane coupling agent (c) exceeds 5.0 mass parts, there exists a possibility of changing NCO / OH group equivalent ratio of a urethane type composition large, and the fall of adhesiveness or fast-curing property is carried out. Bring.
- the compound which has active hydrogen groups such as mercaptosilane and aminosilane, was converted into OH group equivalent, and the thing which has a functional group which reacts with active hydrogen groups, such as isocyanate silane, was converted into NCO group equivalent.
- silanol groups generated by hydrolysis of alkoxysilane contained in the silane coupling agent are not included in the calculation of the OH group equivalent.
- Polyols (d) include polyethylene glycol (PEG), polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), polyether polyols such as sorbitol polyol, polyolefin polyol, poly Examples thereof include siloxane polyols, rosin polyols, acrylic polyols, and polyether polyols, acrylic polyols, polyolefin polyols, or polysiloxane polyols are preferable from the viewpoint of adhesive strength with a polypropylene substrate.
- a polyol (d) may be used individually by 1 type, and may use 2 or more types together.
- olefin polyol examples include polyisoprene polyol, polybutadiene polyol, hydrogenated polyisoprene polyol, and hydrogenated polybutadiene polyol.
- the content of the polyol (d) is 40 to 60% by mass, preferably 40 to 55% by mass, and more preferably 40 to 50% by mass with respect to the total amount of the curing agent (B). preferable.
- the content of the polyol (d) is less than 40% by mass, the NCO / OH group equivalent ratio of the urethane-based composition increases, and good deep curability may not be obtained.
- content of a polyol (d) exceeds 60 mass%, an unreacted component remains and there exists a possibility that favorable adhesiveness and quick curability may no longer be obtained.
- the polyol (d) has a hydroxyl value of 50 to 500 mgKOH / g, preferably 50 to 350 mgKOH / g, more preferably 50 to 200 mgKOH / g.
- the hydroxyl value of the polyol (d) is less than 50 mgKOH / g, the NCO / OH group equivalent ratio of the urethane-based composition is increased, and the mixing ratio of the main agent and the curing agent is 10: 1. , Good deep curability may not be obtained.
- the hydroxyl value of the polyol (d) exceeds 500 mgKOH / g, the NCO / OH group equivalent ratio of the urethane-based composition becomes small, and the mixing mass ratio of the main agent and the curing agent is 3: 1. If it is large, unreacted components remain, and good adhesiveness and fast curability may not be obtained.
- the curing agent (B) may further contain a polyol having a hydroxyl value outside the range of 50 to 500 mgKOH / g.
- amine catalyst (e) As the amine catalyst (e), a known catalyst that accelerates the urethanization reaction or the urethanization reaction can be used.
- the amine catalyst (e) is preferably a tertiary amine from the viewpoint that the urethanization reactivity and ureation reactivity can be enhanced.
- amine catalyst (e) examples include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ′′.
- N ′′ -pentamethyldiethylenetriamine N, N, N ′, N ′′, N ′′ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ′′, N ′′ -penta Methyldipropylenetriamine, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4 0.0] undecene-7, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N-methyl-N ′-(2-dimethylaminoethyl) piperazine, N, N′-dimethylpiperazine, Dimethylcyclohex Silamine, N-methylmorpholine, bis (2-dimethylaminoethyl, N
- the content of the amine catalyst (e) is 1.0 to 10.0% by mass, preferably 1.0 to 8.0% by mass, based on the total amount of the curing agent (B). More preferably, the content is 5 to 5.0% by mass.
- Carbon black (f) preferably has a primary average particle size of 20 to 40 nm, more preferably 25 to 35 nm.
- the average particle diameter of the carbon black is within the predetermined range, the viscosity of the adhesive and the dispersibility of the carbon black are adjusted to a more appropriate range, and the workability and strength of the adhesive are further improved.
- carbon black (f) for example, Asahi # 70 (manufactured by Asahi Carbon Co., Ltd.), Seast 3 (manufactured by Tokai Carbon Co., Ltd., “Seast” is a registered trademark), Mitsubishi Carbon Black # 32 (Mitsubishi) Chemical Co., Ltd.), Niteron # 200 (manufactured by Nisshin Carbon Co., Ltd., “Niteron” is a registered trademark) and the like are suitable. These carbon blacks may be used alone or in combination of two or more.
- the total content of the carbon black (f) is preferably 10 to 30% by mass, and more preferably 10 to 25% by mass with respect to the total amount of the main agent (A) and the curing agent (B).
- the content of the carbon black (g) is within the predetermined range, the strength of the adhesive can be further improved. Further, when uncured, it has thixotropy, improves workability, and cures. It is sometimes preferable because it has foam resistance and, after curing, high strength and high weather resistance due to light shielding effect, that is, durability weather resistance.
- kaolin clay (g) examples include wet kaolin, calcined kaolin, and dry kaolin. From the viewpoint of workability, the total content of kaolin clay (g) is preferably 10 to 35% by mass, and 15 to 25% by mass with respect to the total amount of the main agent (A) and the curing agent (B). More preferably.
- the urethane-based composition of the present embodiment may contain fillers other than kaolin clay, such as talc, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, aluminum hydroxide, magnesium hydroxide, and the like. Good.
- the urethane-based composition of the present embodiment may contain a plasticizer (h).
- the plasticizer (h) include phthalic acid ester compounds, alkyl sulfonic acid ester compounds, and adipic acid ester compounds.
- Specific examples of the phthalic acid ester compounds include dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), butyl benzyl phthalate (BBP), and the like. .
- the urethane-based composition of the present embodiment further includes additives such as pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion-imparting agents, dispersants, and solvents. It may contain.
- the NCO / OH group equivalent ratio which is the abundance ratio of the isocyanate group (NCO) and the hydroxyl group (OH) in the main agent (A) and the curing agent (B) is 1.0 to 5.0.
- NCO / OH group equivalent ratio is less than 1.0, when the main agent and the curing agent are mixed, the proportion of the unreacted polyol increases, resulting in uncured or insufficient adhesive properties.
- the NCO / OH group equivalent ratio exceeds 5.0, when the main agent and the curing agent are mixed, the presence ratio of isocyanate and prepolymer increases, resulting in an increase in the amount of reaction with moisture in the air. , Fast curability and deep curability are impaired.
- Main agents # 1 to 6 and curing agents # 1 to 6 were prepared by the following method.
- the main agents # 1 to # 3 and the curing agents # 1 to 3 correspond to Examples 1 to 3, respectively, and the main agents # 4 to 6 and the curing agents # 4 to 6 correspond to Comparative Examples 1 to 3, respectively.
- Premixol 3012 polyether polyol manufactured by Asahi Glass Co., Ltd., number average molecular weight (Mn) 12000, trifunctional, hydroxyl value 14.0 mgKOH / g
- Mn number average molecular weight
- Millionate MT monomeric MDI (diphenylmethane diisocyanate) manufactured by Tosoh Corporation, “Millionate” is a registered trademark, NCO 33.6% by mass
- tin catalyst Nikka octyne tin
- Main agents # 2 to 6 were prepared in the same manner as main agent # 1.
- ⁇ Preparation of curing agent> (Curing agent # 1) In a kneading vessel equipped with a stirrer, a nitrogen introduction tube, a vacuum pump, and a heating / cooling device, 88.0 g of R-15HT (polybutadiene polyol, 2.3 functional, hydroxyl value 103 mgKOH / g, manufactured by Idemitsu Kosan Co., Ltd.), Preminol 7012 (Asahi Glass) 12.0 g of polyether polyol, trifunctional, hydroxyl value 16.8 mgKOH / g) manufactured by Co., Ltd., 2 EDP-300 (modified diamine propylene oxide, tetrafunctional, 760 mgKOH / g, manufactured by ADEKA Corporation) .0 g, Asahi # 70 (carbon black manufactured by Asahi Carbon Co., Ltd., 41.0 g of primary particle diameter 28 nm) and 67.0 g of Iceberg K (calcined clay manufactured by Shirai
- the kneading vessel was heated until the contents reached 100 ° C., and the pressure was reduced until the inside of the kneading vessel became 20 mmHg by a vacuum pump, and stirring was continued for 1 hour. Further, the content was cooled to 40 ° C., 6.0 g of U-CAT660M (an amine catalyst manufactured by San Apro Co., Ltd.) was added, and the mixture was stirred for 10 minutes.
- U-CAT660M an amine catalyst manufactured by San Apro Co., Ltd.
- (Curing agent # 2) UT-1001 (polyfunctional hydroxyacrylic polymer manufactured by Soken Chemical Co., Ltd., hydroxyl value 58 mgKOH / g) 100.0 g, EDP-300 (Co., Ltd.) 2.0 g of modified ethylenediaminepropylene oxide made by ADEKA, tetrafunctional, hydroxyl value 760 mgKOH / g), 41.0 g of Asahi # 70 (carbon black produced by Asahi Carbon Co., Ltd., primary particle size 28 nm), Iceberg K ( 67.0 g of calcined clay manufactured by Shiraishi Calcium Co., Ltd. was charged, and stirred for 30 minutes until there was no lump of carbon black and calcined clay.
- Asahi # 70 carbon black produced by Asahi Carbon Co., Ltd., primary particle size 28 nm
- Iceberg K 67.0 g of calcined clay manufactured by Shiraishi Calcium Co., Ltd. was charged, and stirred for 30 minutes until there was no
- the kneading vessel was heated until the contents reached 100 ° C., and the pressure was reduced until the inside of the kneading vessel became 20 mmHg by a vacuum pump, and stirring was continued for 1 hour. Further, the content was cooled to 40 ° C., 6.0 g of U-CAT660M (an amine catalyst manufactured by San Apro Co., Ltd.) was added, and the mixture was stirred for 10 minutes.
- U-CAT660M an amine catalyst manufactured by San Apro Co., Ltd.
- Premixol 7012 polyether polyol, trifunctional, hydroxyl value 16.8 mgKOH / g, manufactured by Asahi Glass Co., Ltd.
- 100.0 g EDP-300 (stock) in a kneading vessel equipped with a stirrer, nitrogen inlet tube, vacuum pump and heating / cooling device 2.0 g of modified ethylenediaminepropylene oxide, tetrafunctional, hydroxyl value 760 mgKOH / g) manufactured by ADEKA, 41.0 g of Asahi # 70 (carbon black manufactured by Asahi Carbon Co., Ltd., primary particle size 28 nm), Iceberg K 67.0 g of (calcined clay manufactured by Shiroishi Calcium Co., Ltd.) was charged and stirred for 30 minutes until there was no lump of carbon black and kaolin clay.
- the kneading vessel was heated until the contents reached 100 ° C., and the pressure was reduced until the inside of the kneading vessel became 20 mmHg by a vacuum pump, and stirring was continued for 1 hour. Further, the content was cooled to 40 ° C., 6.0 g of U-CAT660M (an amine catalyst manufactured by San Apro Co., Ltd.) was added, and the mixture was stirred for 10 minutes.
- U-CAT660M an amine catalyst manufactured by San Apro Co., Ltd.
- Table 1 summarizes the composition (unit: parts by mass) of the main agents # 1 to # 6 and the curing agents # 1 to # 6.
- Non-primer adhesion Two sheets of polypropylene base material subjected to frame treatment were prepared.
- the main agent and the curing agent corresponding to Examples 1 to 3 and Comparative Examples 1 to 3 were mixed at a predetermined mixing ratio using a planetary device, and the resulting mixture was mixed with one substrate at a thickness of 3 mm.
- a test piece was prepared by pasting and pressing the surface of the other substrate so that the adhesion area was 250 mm 2 (25 mm ⁇ 10 mm).
- the prepared test piece was allowed to stand at 23 ° C. and 50% RH (relative humidity) for 72 hours for curing to obtain a cured test piece.
- test piece was subjected to a tensile test according to JIS K6850: 1999 at 23 ° C., the shear strength was measured, and the fracture strength was recorded.
- the adhesive was uncured, it was evaluated as “uncured” and no measurement was performed. Further, the fracture state was visually confirmed, and “CF” was indicated when the adhesive was cohesive and “AF” was indicated when the interface was peeled between the base material and the adhesive.
- the urethane-based compositions of Examples 1 to 3 have excellent rapid curability and deep part regardless of the mixing mass ratio of the main agent and the curing agent in the range of 10: 1 to 3: 1. It has curability and non-primer adhesion. Moreover, it turns out that it exists in the tendency which is excellent in adhesive strength, so that there is much quantity of a main ingredient.
- the urethane-based compositions of Comparative Examples 1 to 3 have a mixing mass ratio of the main agent and the curing agent in the range of 10: 1 to 3: 1, and at least one of fast curing, deep curing and non-primer adhesiveness. It has been clarified that there is a blending ratio in which such physical properties are lowered.
Abstract
Description
ウレタン系組成物としては、空気中の湿気等によって硬化する、湿気硬化型と呼ばれる一液型の組成物と、主剤と硬化剤とからなる二液型の組成物が知られている。これらのうち、接着工程における作業性の観点から、可使時間(ポットライフ、多液塗料において化学反応等で塗料が硬化し始めるまでの時間)を十分確保でき、且つ速硬化が可能となる二液型が好まれる。
しかし近年、ウレタン系組成物の接着において、工程簡略化及び作業環境改善の観点から、ノンプライマー処理化が求められている。特に、プライマー処理工程の排除(レス化)は、組み立て工程のタクト管理が厳しい、自動車製造工程で顕著な要請である。
また、二液硬化型接着剤を実際に使用する観点からは、主剤と硬化剤の混合比(配合比)を変えた場合であっても、幅広い混合比で優れた性能を発揮することが望ましい。さらに、二液硬化型接着剤においては主剤と硬化剤の混合質量比が1:1に限定されている場合も多いが、接着強度を向上させる観点から、主剤の配合量を増やしたときに優れた性能を発揮することが望ましい。
[1] 主剤(A)及び硬化剤(B)を含む二液硬化型ウレタン系組成物であって、
主剤(A)は、ウレタンプレポリマー(a)、ポリイソシアネート化合物のイソシアヌレート変性体(b)及びシランカップリング剤(c)を含有し、ポリイソシアネート化合物のイソシアヌレート変性体(b)の含有量はウレタンプレポリマー(a)100質量部に対して0.5~3.0質量部であり、シランカップリング剤(c)の含有量はウレタンプレポリマー(a)100質量部に対して0.5~5.0質量部であり、
硬化剤(B)は、50~500mgKOH/gの水酸基価を有するポリオール(d)及びアミン触媒(e)を含有し、ポリオール(d)の含有量は硬化剤(B)の総量に対して40~60質量%であり、アミン触媒(e)の含有量は硬化剤(B)の総量に対して1.0~10.0質量%であり、
主剤(A)及び硬化剤(B)の混合質量比が3:1~10:1であり、且つ
主剤(A)及び硬化剤(B)中のNCO/OH基当量比が1.0~5.0である二液硬化型ウレタン系組成物。
[2] 主剤(A)及び硬化剤(B)の少なくとも一方がカーボンブラック(f)をさらに含有し、カーボンブラック(f)の総含有量が主剤(A)及び硬化剤(B)の総量に対して10~30質量%である、[1]に記載の二液硬化型ウレタン系組成物。
[3] 主剤(A)及び硬化剤(B)の少なくとも一方がカオリンクレー(g)をさらに含有し、カオリンクレー(g)の総含有量が主剤(A)及び硬化剤(B)の総量に対して10~35質量%である、[1]又は[2]に記載の二液硬化型ウレタン系組成物。
[4] ウレタンプレポリマー(a)が、数平均分子量8000以上のポリエーテルポリオール(a-1)とジフェニルメタンジイソシアネート(a-2)の反応生成物である、[1]~[3]のいずれかに記載の二液硬化型ウレタン系組成物。
ウレタンプレポリマー(a)は、活性水素基を2個以上有する化合物とイソシアネート基を2個以上有するポリイソシアネート化合物との反応生成物である。本実施形態のウレタンプレポリマーは、イソシアネート基の数が過剰となるように反応させて、分子内にイソシアネート基を有するものであることが好ましい。
活性水素基としては、例えば、ヒドロキシ基(OH基)、カルボキシル基(COOH基)、アミノ基(NH2基)、チオール基(SH基)等が挙げられる。活性水素基を2個以上有する化合物としては、ポリオールが好ましく、ポリエーテルポリオール(a-1)がより好ましい。
ポリイソシアネート化合物としては、イソシアネート基が芳香族炭化水素と結合している芳香族ポリイソシアネート、イソシアネート基が脂環式炭化水素と結合している脂環族ポリイソシアネート等が挙げられる。これらの中で、芳香族ポリイソシアネートが好ましく、ジフェニルメタンジイソシアネート(a-2)又はジシクロヘキシルメタンジイソシアネート(H12MDI)がより好ましく、ジフェニルメタンジイソシアネート(a-2)がさらに好ましい。
活性水素基を2個以上有する化合物及びイソシアネート基を2個以上有するポリイソシアネート化合物は、それぞれ1種を単独で用いてもよく、2種以上を併用してもよい。
上記ポリエーテルポリオール(a-1)は、OH基を2個以上有するポリエーテルポリオールであれば特に限定されない。具体的には、ポリエチレングリコール(PEG)、ポリプロピレングリコール(PPG)、エチレンオキサイド/プロピレンオキサイド共重合体、ポリテトラメチレンエーテルグリコール(PTMEG)、ソルビトール系ポリオール等が挙げられる。これらの中でもポリプロピレングリコール(PPG)が好ましい。また、ポリエーテルポリオール(a-1)は1種を単独で用いてもよく、2種以上を併用してもよい。
なお、本明細書中、「数平均分子量」とは、ゲル浸透クロマトグラフィー(GPC)を利用し、標準ポリスチレンの検量線を使用して算出したものである。
GPC測定条件は、下記のとおりである。
・測定器 :ACQUITY UPLC APCシステム(Waters社製)
・カラム :APC XT-900、APC XT-200、APC XT-125、APC XT-45 (Waters社製)
・キャリア:テトラヒドロフラン(THF)
・検出器 :示差屈折
・サンプル:0.5質量%THF溶液
・検量線 :ポリスチレン
上記ジフェニルメタンジイソシアネート(a-2)としては、例えば、4,4’-ジフェニルメタンジイソシアネート(4,4’-MDI(モノメリックMDI))、2,4’-ジフェニルメタンジイソシアネート)(2,4’-MDI)等が挙げられる。
上記ポリイソシアネート化合物のイソシアヌレート変性体(b)は、トルエンジイソシアネート(TDI)、ヘキサメチレンジイソシアネート(HDI)、キシリレンジイソシアネート(XDI)、ナフタレンジイソシアネート(NDI)、イソホロンジイソシアネート(IPDI)等の各種ポリジイソシアネート化合物の3量体である。当該3量体は、1種のポリイソシアネート化合物の3量体であってもよく、2種以上のポリイソシアネート化合物、例えばHDIとTDIとの混合3量体であってもよい。当該3量体の末端官能基は3官能全てがイソシアネート基(NCO基)である。
ノンプライマー接着性を向上させることができる理由は、ポリイソシアネート化合物のイソシアヌレート変性体の分子内に3個存在するイソシアネート基(-NCO)がウレタン系組成物中にてウレタン結合を形成し、さらに、ポリプロピレン基材表面にフレーム処理を施すことによって導入された極性基ともウレタン結合を形成する結果、界面接着力を強くすると推測される。
また、耐湿熱老化性を向上させることができる理由は、ポリイソシアネート化合物のイソシアヌレート変性体の化合物中に存在するイソシアヌレート環がウレタン系組成物中の凝集力発現に寄与するためであると推測される。
シランカップリング剤(c)は、1つの分子中に反応性の異なる2種類の官能基を有する有機ケイ素化合物である。シランカップリング剤(c)としては、例えば、エポキシシラン、ビニルシラン、イミダゾールシラン、メルカプトシラン、アミノシラン、スチリルシラン、イソシアネートシラン、スルフィドシラン、ウレイドシラン等が挙げられ、ウレタン系組成物に含有し、ノンプライマー接着性を得るには、メルカプトシラン、アミノシラン、スルフィドシラン、イソシアネートシランが好適である。
シランカップリング剤(c)の含有量が0.5質量部未満となると、ウレタン系組成物とポリプロピレン基材の間の密着力が小さくなり、結果的に特に高温下でのノンプライマー接着性が小さくなる。また、シランカップリング剤(c)の含有量が5.0質量部を超えると、ウレタン系組成物のNCO/OH基当量比を大きく変動させるおそれがあり、接着性又は速硬化性の低下をもたらす。
なお、メルカプトシラン、アミノシラン等の活性水素基を有する化合物はOH基当量に換算し、イソシアネートシラン等の活性水素基と反応する官能基を有するものに関してはNCO基当量に換算した。また、シランカップリング剤が有するアルコキシシランの加水分解によって生じるシラノール基はOH基当量の計算に含まないものとする。
ポリオール(d)としては、ポリエチレングリコール(PEG)、ポリプロピレングリコール(PPG)、エチレンオキサイド/プロピレンオキサイド共重合体、ポリテトラメチレンエーテルグリコール(PTMEG)、ソルビトール系ポリオール等のポリエーテルポリオール、ポリオレフィンポリオール、ポリシロキサンポリオール、ロジンポリオール、アクリルポリオールなどが挙げられ、ポリプロピレン基材との接着力の観点から、ポリエーテルポリオール、アクリルポリオール、ポリオレフィンポリオール又はポリシロキサンポリオールが好適である。ポリオール(d)は、1種を単独で用いてもよく、2種以上を併用してもよい。
ポリオール(d)の水酸基価が50mgKOH/g未満となると、ウレタン系組成物のNCO/OH基当量比が大きくなり、主剤と硬化剤の混合質量比が10:1等主剤の割合が大きい場合に、良好な深部硬化性が得られないおそれがある。また、ポリオール(d)の水酸基価が500mgKOH/gを超えると、ウレタン系組成物のNCO/OH基当量比が小さくなり、主剤と硬化剤の混合質量比が3:1等硬化剤の割合が大きい場合に、未反応成分が残り、良好な接着性、速硬化性が得られなくなるおそれがある。
アミン触媒(e)としては、ウレタン化反応又は尿素化反応を促進する公知の触媒が使用できる。アミン触媒(e)は、ウレタン化反応性及び尿素化反応性を高めることができる点から、三級アミンであることが好ましい。
特にイミダゾール系アミン化合物は、速硬化性かつオープンタイムを両立する上で好ましい。
上記アミン触媒(e)は1種を単独で用いてもよく、2種以上を併用してもよい。
カーボンブラック(f)は、その一次平均粒子径が20~40nmであることが好ましく、25~35nmであることがより好ましい。カーボンブラックの平均粒子径が上記所定の範囲であることにより、接着剤の粘性及びカーボンブラックの分散性がより適切な範囲に調整され、接着剤の作業性及び強度がより向上する。
カオリンクレー(g)としては、例えば、湿式カオリン、焼成カオリン、乾式カオリン等が挙げられる。カオリンクレー(g)の総含有量は、作業性の観点から、主剤(A)と硬化剤(B)の総量に対して、10~35質量%であることが好ましく、15~25質量%であることがより好ましい。
本実施形態のウレタン系組成物は、可塑剤(h)を含有していてもよい。可塑剤(h)としては、例えばフタル酸エステル系化合物、アルキルスルホン酸エステル系化合物、アジピン酸エステル系化合物等が挙げられる。フタル酸エステル系化合物の具体例としては、フタル酸ジオクチル(DOP)、フタル酸ジブチル(DBP)、フタル酸ジイソノニル(DINP)、フタル酸ジイソデシル(DIDP)、フタル酸ブチルベンジル(BBP)等が挙げられる。
以下に示す方法で、主剤#1~6及び硬化剤#1~6を調製した。なお、主剤#1~3及び硬化剤#1~3がそれぞれ実施例1~3に対応し、主剤#4~6及び硬化剤#4~6がそれぞれ比較例1~3に対応する。
(主剤#1)
撹拌機、窒素導入管、真空ポンプ及び加熱冷却装置付き混練容器にプレミノール3012(旭硝子株式会社製のポリエーテルポリオール、数平均分子量(Mn)12000、3官能、水酸基価14.0mgKOH/g)を90.9g、三菱カーボンブラック#32(三菱化学株式会社製のカーボンブラック、一次粒子径28nm)を40g、アイスバーグK(白石カルシウム株式会社製の焼成クレー)を21.0g、DINP(株式会社ジェイプラス製のフタル酸ジイソノニル)を2.7g仕込み、30分、カーボンブラック、焼成クレーの塊が無くなるまで撹拌した。次いで、内容物が100℃になるまで混練容器を加熱し、真空ポンプにより混練容器内部が20mmHgになるまで低圧にし、1時間撹拌し続けた。さらに、内容物の温度が70℃になるまで冷却し、容器内にミリオネートMT(東ソー株式会社製のモノメリックMDI(ジフェニルメタンジイソシアネート)、「ミリオネート」は登録商標、NCO33.6質量%)を9.1g、錫触媒(ニッカオクチック錫)を200ppm添加し、窒素導入後、1時間撹拌し続けた。さらに、内容物の温度が40℃になるまで冷却し、KBM-803(信越化学工業株式会社製のシランカップリング剤メルカプトシラン、活性水素当量196g/eq)を1.8g、スミジュールN3300(住化バイエルウレタン株式会社製のHDIイソシアヌレート変性体、NCO25.0質量%)を1.8g添加し、10分攪拌した。なお、上記工程で得られたプレミノール3012とミリオネートMTの反応物をウレタンプレポリマーとした。
主剤#1と同様の方法で、主剤#2~6を調製した。
(硬化剤#1)
撹拌機、窒素導入管、真空ポンプ及び加熱冷却装置付き混練容器にR-15HT(出光興産株式会社製のポリブタジエンポリオール、2.3官能、水酸基価103mgKOH/g)を88.0g、プレミノール7012(旭硝子株式会社製のポリエーテルポリオール、3官能、水酸基価16.8mgKOH/g)を12.0g、EDP-300(株式会社ADEKA製のエチレンジアミンプロピレンオキサイド変性体、4官能、水酸基価760mgKOH/g)を2.0g、旭#70(旭カーボン株式会社製のカーボンブラック、一次粒子径28nm)を41.0g、アイスバーグK(白石カルシウム株式会社製の焼成クレー)を67.0g仕込み、30分、カーボンブラック、焼成クレーの塊が無くなるまで撹拌した。次いで、内容物が100℃になるまで混練容器を加熱し、真空ポンプにより混練容器内部が20mmHgになるまで低圧にし、1時間撹拌し続けた。さらに、内容物の温度が40℃になるまで冷却し、U-CAT660M(サンアプロ株式会社製のアミン触媒)を6.0g添加し、10分攪拌した。
撹拌機、窒素導入管、真空ポンプ及び加熱冷却装置付き混練容器にUT-1001(綜研化学株式会社製の多官能ヒドロキシアクリルポリマー、水酸基価58mgKOH/g)を100.0g、EDP-300(株式会社ADEKA製のエチレンジアミンプロピレンオキサイド変性体、4官能、水酸基価760mgKOH/g)を2.0g、旭#70(旭カーボン株式会社製のカーボンブラック、一次粒子径28nm)を41.0g、アイスバーグK(白石カルシウム株式会社製の焼成クレー)を67.0g仕込み、30分、カーボンブラック、焼成クレーの塊が無くなるまで撹拌した。次いで、内容物が100℃になるまで混練容器を加熱し、真空ポンプにより混練容器内部が20mmHgになるまで低圧にし、1時間撹拌し続けた。さらに、内容物の温度が40℃になるまで冷却し、U-CAT660M(サンアプロ株式会社製のアミン触媒)を6.0g添加し、10分攪拌した。
撹拌機、窒素導入管、真空ポンプ及び加熱冷却装置付き混練容器にエクセノール720(旭硝子株式会社製のポリエーテルポリオール、2官能、水酸基価160mgKOH/g)を10.0g、エクセノール2020(旭硝子株式会社製のポリエーテルポリオール、2官能、水酸基価56mgKOH/g)を90.0g、EDP-300(株式会社ADEKA製のエチレンジアミンプロピレンオキサイド変性体、4官能、水酸基価760mgKOH/g)を2.0g、旭#70(旭カーボン株式会社製のカーボンブラック、一次粒子径28nm)を41.0g、アイスバーグK(白石カルシウム株式会社製の焼成クレー)を67.0g仕込み、30分、カーボンブラック、焼成クレーの塊が無くなるまで撹拌した。次いで、内容物が100℃になるまで混練容器を加熱し、真空ポンプにより混練容器内部が20mmHgになるまで低圧にし、1時間撹拌し続けた。さらに、内容物の温度が40℃になるまで冷却し、U-CAT660M(サンアプロ株式会社製のアミン触媒)を6.0g添加し、10分攪拌した。
撹拌機、窒素導入管、真空ポンプ及び加熱冷却装置付き混練容器にエクセノール720(旭硝子株式会社製のポリエーテルポリオール、2官能、水酸基価160mgKOH/g)を77.0g、エクセノール1030(旭硝子株式会社製のポリエーテルポリオール、3官能、水酸基価168mgKOH/g)を23.0g、EDP-300(株式会社ADEKA製のエチレンジアミンプロピレンオキサイド変性体、4官能、水酸基価760mgKOH/g)を2.0g、旭#70(旭カーボン株式会社製のカーボンブラック、一次粒子径28nm)を41.0g、アイスバーグK(白石カルシウム株式会社製の焼成クレー)を67.0g仕込み、30分、カーボンブラック、焼成クレーの塊が無くなるまで撹拌した。次いで、内容物が100℃になるまで混練容器を加熱し、真空ポンプにより混練容器内部が20mmHgになるまで低圧にし、1時間撹拌し続けた。さらに、内容物の温度が40℃になるまで冷却し、U-CAT660M(サンアプロ株式会社製のアミン触媒)を6.0g添加し、10分攪拌した。
撹拌機、窒素導入管、真空ポンプ及び加熱冷却装置付き混練容器にプレミノール7012(旭硝子株式会社製のポリエーテルポリオール、3官能、水酸基価16.8mgKOH/g)を100.0g、EDP-300(株式会社ADEKA製のエチレンジアミンプロピレンオキサイド変性体、4官能、水酸基価760mgKOH/g)を2.0g、旭#70(旭カーボン株式会社製のカーボンブラック、一次粒子径28nm)を41.0g、アイスバーグK(白石カルシウム株式会社製の焼成クレー)を67.0g仕込み、30分、カーボンブラック、カオリンクレーの塊が無くなるまで撹拌した。次いで、内容物が100℃になるまで混練容器を加熱し、真空ポンプにより混練容器内部が20mmHgになるまで低圧にし、1時間撹拌し続けた。さらに、内容物の温度が40℃になるまで冷却し、U-CAT660M(サンアプロ株式会社製のアミン触媒)を6.0g添加し、10分攪拌した。
撹拌機、窒素導入管、真空ポンプ及び加熱冷却装置付き混練容器にEDP-1100(株式会社ADEKA製のエチレンジアミンプロピレンオキサイド変性体、4官能、水酸基価214mgKOH/g)を51.0g、EDP-300(株式会社ADEKA製のエチレンジアミンプロピレンオキサイド変性体、数平均分子量300、4官能、水酸基価760mgKOH/g)を51.0g、旭#70(旭カーボン株式会社製のカーボンブラック、一次粒子径28nm)を41.0g、アイスバーグK(白石カルシウム株式会社製の焼成クレー)を67.0g仕込み、30分、カーボンブラック、カオリンクレーの塊が無くなるまで撹拌した。次いで、内容物が100℃になるまで混練容器を加熱し、真空ポンプにより混練容器内部が20mmHgになるまで低圧にし、1時間撹拌し続けた。さらに、内容物の温度が40℃になるまで冷却し、U-CAT660M(サンアプロ株式会社製のアミン触媒)を6.0g添加し、10分攪拌した。
上述の主剤及び硬化剤を用いて、深部硬化性、速硬化性及びノンプライマー接着性を以下に示す方法で評価した。なお、主剤と硬化剤の混合質量比は、10:1、6:1及び3:1の3とおりとした。
上記実施例1~3及び比較例1~3に対応する主剤と硬化剤を上記所定の配合比でプラネタリ装置を用いて混合した。得られた混合物を、直径3cm×高さ3cmの円錐状のポリプロピレン製の容器の中に流し込み、養生のために23℃、50%RH(相対湿度)にて72時間放置し、養生後のサンプルを得た。得られたサンプルを半円状になるようナイフで半分に切断し、断面のタックを評価した。
深部硬化性の評価として、断面のタックが無かった場合は「A」、わずかなタックが残っていた場合は「B」、未硬化もしくは多くのタックが残っていた場合は「C」とした。
上記実施例1~3及び比較例1~3に対応する主剤と硬化剤を上記所定の混合比でプラネタリ装置を用いて混合した。得られた混合物を、フレーム処理を行ったポリプロピレン基材に直接ビード状に塗布し、これに離型紙を重ね接着剤厚さが3mmとなるように圧着した後、養生のために60℃乾燥機に10分間投入し、速硬化性測定サンプルを得た。このサンプルに対して、ナイフカットによる剥離試験を行い、速硬化性を評価した。
接着剤の接着性評価として、接着した部分が凝集破壊の場合は「A」、ポリプロピレン基材表面と接着剤間との界面破壊の場合は「B」とした。
フレーム処理を行ったポリプロピレン基材を2枚用意した。上記実施例1~3及び比較例1~3に対応する主剤と硬化剤を上記所定の混合比でプラネタリ装置を用いて混合し、得られた混合物を、一方の基材に3mmの厚さで塗布した。接着面積が250mm2(25mm×10mm)になるように他方の基材の表面と張り合わせ、圧着させることで試験片を作製した。
作製した試験片を養生のために23℃、50%RH(相対湿度)にて72時間放置し、養生後の試験片を得た。この試験片に対して、23℃下でJIS K6850:1999に準じた引張試験を行い、せん断強度を測定し、破壊強度を記録した。接着剤が未硬化の場合は「未硬化」と評価し、測定は行わなかった。また、破壊状態は目視で確認し、接着剤が凝集破壊している場合は「CF」、基材―接着剤間で界面剥離している場合は「AF」とした。
Claims (4)
- 主剤(A)及び硬化剤(B)を含む二液硬化型ウレタン系組成物であって、
主剤(A)は、ウレタンプレポリマー(a)、ポリイソシアネート化合物のイソシアヌレート変性体(b)及びシランカップリング剤(c)を含有し、ポリイソシアネート化合物のイソシアヌレート変性体(b)の含有量はウレタンプレポリマー(a)100質量部に対して0.5~3.0質量部であり、シランカップリング剤(c)の含有量はウレタンプレポリマー(a)100質量部に対して0.5~5.0質量部であり、
硬化剤(B)は、50~500mgKOH/gの水酸基価を有するポリオール(d)及びアミン触媒(e)を含有し、ポリオール(d)の含有量は硬化剤(B)の総量に対して40~60質量%であり、アミン触媒(e)の含有量は硬化剤(B)の総量に対して1.0~10.0質量%であり、
主剤(A)及び硬化剤(B)の混合質量比が3:1~10:1であり、且つ
主剤(A)及び硬化剤(B)中のNCO/OH基当量比が1.0~5.0である二液硬化型ウレタン系組成物。 - 主剤(A)及び硬化剤(B)の少なくとも一方がカーボンブラック(f)をさらに含有し、カーボンブラック(f)の総含有量が主剤(A)及び硬化剤(B)の総量に対して10~30質量%である、請求項1に記載の二液硬化型ウレタン系組成物。
- 主剤(A)及び硬化剤(B)の少なくとも一方がカオリンクレー(g)をさらに含有し、カオリンクレー(g)の総含有量が主剤(A)及び硬化剤(B)の総量に対して10~35質量%である、請求項1又は2に記載の二液硬化型ウレタン系組成物。
- ウレタンプレポリマー(a)が、数平均分子量8000以上のポリエーテルポリオール(a-1)とジフェニルメタンジイソシアネート(a-2)の反応生成物である、請求項1~3のいずれか一項に記載の二液硬化型ウレタン系組成物。
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EP3950873A4 (en) * | 2019-04-05 | 2022-04-06 | Showa Denko Materials Co., Ltd. | SET OF ADHESIVE AGENTS AND METHOD FOR MAKING A STRUCTURAL BODY |
JP7328756B2 (ja) | 2018-12-27 | 2023-08-17 | 理想科学工業株式会社 | 感熱スクリーンマスター用接着剤、感熱スクリーンマスター及び感熱スクリーンマスターの製造方法 |
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KR102130698B1 (ko) * | 2020-03-12 | 2020-07-07 | 신백범 | 이액형 폴리우레탄계 조성물을 포함하는 pvc 창호 프레임 |
CN112375530B (zh) * | 2020-11-26 | 2022-10-28 | Sika技术股份公司 | 减少起泡且具有哑光效果的聚氨酯组合物 |
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- 2017-03-29 CN CN201780088948.9A patent/CN110494495A/zh active Pending
- 2017-03-29 KR KR1020197024025A patent/KR102289291B1/ko active IP Right Grant
- 2017-03-29 WO PCT/JP2017/013059 patent/WO2018179178A1/ja unknown
- 2017-03-29 JP JP2019508459A patent/JP6943280B2/ja active Active
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EP3950873A4 (en) * | 2019-04-05 | 2022-04-06 | Showa Denko Materials Co., Ltd. | SET OF ADHESIVE AGENTS AND METHOD FOR MAKING A STRUCTURAL BODY |
Also Published As
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US20200024449A1 (en) | 2020-01-23 |
JP6943280B2 (ja) | 2021-09-29 |
US11479667B2 (en) | 2022-10-25 |
CN110494495A (zh) | 2019-11-22 |
EP3604444A4 (en) | 2020-12-16 |
KR102289291B1 (ko) | 2021-08-13 |
JPWO2018179178A1 (ja) | 2020-01-30 |
EP3604444A1 (en) | 2020-02-05 |
KR20190129836A (ko) | 2019-11-20 |
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