Adhesive

Abstract

To provide a suitable alternative condensation-curable SMP based adhesive composition, which upon cure does not minimize or prevent functions of an anti-haze treated material surface.SOLUTION: There is provided a two-part condensation-curable silyl-modified polymer based adhesive composition in particular for use in bonding a front lens having an anti-haze coating onto a lamp body for lighting applications. A lamp comprises a lamp body and a front lens, utilizing the adhesive composition to bond the lens to the lamp body while preserving the integrity of the anti-haze coating.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure particularly provides a condensation-curable silyl-modified polymer (SMP)-based adhesive for use in adhering a front lens onto a lamp body for lighting applications, and relates to a lamp comprising a lamp body and a front lens, and using the adhesive to adhere the lens to the lamp body.

[0002] Condensation-curable SMP-based adhesives are used in various lighting and window applications. By way of example, these can be used as adhesives for anti-fog windows, adhesives for lenses for lighting applications, and / or adhesives for transparent covers for lighting applications such as automotive lighting, road lighting, outdoor lighting. Of particular importance is their use in "high-efficiency" lighting systems, such as light-emitting diode (LED) applications, organic LED applications, fluorescent lighting applications, vapor gas discharge lighting applications, and neon lamp applications.

[0003] One of the characteristics of high-efficiency lighting applications is that the heat generated thereby is less than that of conventional light sources. These high-efficiency lighting systems are often provided in an enclosed housing. A lighting unit, for example, an automotive headlamp, often comprises a lamp body defining a lamp chamber, and a front lens designed to fit and engage with a front opening and sealed in place by an adhesive, such as a condensation-curable organosiloxane-based adhesive. A discharge lamp bulb located within the lamp chamber serves as a light source.

[0004] The front lens is typically transparent and can be made from various materials, such as polymethyl methacrylate (PMMA) or polycarbonate resin. Such resins can be molded, extruded, and / or thermoformed, for example, to make a front lens for a lighting unit, and can also improve the overall transparency and transmissivity of the lighting system. However, products made from polycarbonate and other resins suitable for manufacturing these lenses typically have a hydrophobic surface. The hydrophobic nature of these surfaces can be a problem when used as a transparent front cover within a sealed lighting unit, such as within an LED system, and when used as other light-emitting devices with less heat, for example, when the polycarbonate material is used for its optical quality, high refractive index (RI), and / or optical transparency. The reason for this is that moisture / water droplets / particles on the resin surface tend to accumulate, reducing the transparency and / or transmissivity of visible light passing through the material, especially when accumulated on the inner surface of a transparent front cover within a sealed lighting unit, such as within a headlamp, which is called cold fogging or cold hazing in the industry.

[0005] Unfortunately, while highly efficient lighting systems save energy, a side effect of their introduction is that, as previously shown, the heat generated thereby is reduced, and consequently the moisture accumulated on the surfaces of these lighting systems is less likely to evaporate during use. The accumulation of moisture, etc., on the inner surface of the transparent cover of the above lamp unit is called "fogging" or "hazing" in the industry. These terms are effectively interchangeable, but will be referred to as hazing hereafter.

[0006] Assume that the front lens of a headlamp is made of a material having a hydrophobic surface such as polycarbonate resin (PC). Then, the inner surface of the front lens is hydrophobic and is sealed inside the lamp body. However, an automotive headlamp can have openings for pressure equalization although it is not hermetically sealed. These openings are sealed by a film that allows air and humidity to move in and out of the headlamp. Under certain environmental conditions (e.g., low temperature but high humidity), the humidity inside the headlamp may condense on the inner hydrophobic surface of the front lens in the form of very fine droplets, resulting in an appearance of a hazy film (or fog) from the outside and a degradation in the quality of the illumination emitted from the lamp through the front lens.

[0007] Several solutions have been developed to combat this hazing or fogging problem. Perhaps the most common one is the application of an anti-hazing coating (AHC) on the inner surface of the front lens. When applied to the inner surface of the lens, the AHC forms a hydrophilic surface coating thereon, which, while condensation may still occur on the surface, allows water to form a thin film that becomes invisible to the end-user. However, when a headlamp with an AHC-coated inner surface of the lens is sealed with a standard silicone adhesive, the hydrophilicity of the AHC is destroyed after a short time due to degassing and volatile substances released from the silicone adhesive that may interact with the AHC.

[0008] A wide range of components can be incorporated into such commercially available hydrophilic anti-fog / hazing coating compositions, which are designed to maximize the surface energy of the inner surface of such a front cover. These can include, for example, hydrophilic organic substances such as methyl methacrylate, diethylene glycol - monomethyl ether methacrylate, as well as hydrogels and gelatin.

[0009] Another solution is to introduce an anti-haze additive, such as a surfactant, into the resin itself during the manufacture of the lens. These are intended to function in the same way as a coating, but there is no need to apply such a coating on the inner surface of the lens, i.e., by providing a hydrophilic surface, it is intended that no mist, condensation, or other forms of hazing occur on the said inner surface of the lens.

[0010] Examples of these additives include sorbitan esters, ethoxylated sorbitan esters, polyol esters, and glycerol esters. Such additives have been successfully introduced into polyethylene and poly(vinyl chloride) materials used in some anti-fogging articles, avoiding the need for an anti-haze coating. However, they have generally been found to be unsuitable for use in polycarbonate and aromatic thermoplastic polymers.

[0011] As a result, such transparent polymer surfaces are often treated with one or more coatings to provide anti-fogging performance and scratch or abrasion resistance. Lens coatings can be applied in different ways, such as using a dip coating process or a spin coating process. Multiple coatings may also be required to obtain other properties such as mirror coatings, as well as anti-smudging and anti-fouling properties.

[0012] As mentioned above, a transparent front lens for a lighting unit is generally designed to fit and engage with the front opening of the lamp chamber and is sealed in place using an adhesive to form a sealed unit. Considering the physical properties, condensation-curing silicone-based adhesives are one of the most preferred adhesives for this application. They are excellent in the role of an adhesive, while a condensation-curing mechanism for causing curing and a preferred selection of a cross-linking agent result in the generation of chemical by-products during the curing process inside the sealed unit.

[0013] The composition typically includes an -OH terminated polydimethylsiloxane polymer and a crosslinking agent such as methyltrimethoxysilane (having reactive methoxy groups that interact with the -OH groups from the polydimethylsiloxane polymer), and methanol is produced as a byproduct during the curing process. The condensation byproducts and residual crosslinking agent materials often deposit on the AHC-treated inner surface of the front lens, and this deposition on the resulting anti-haze coating can reduce the effectiveness of the anti-haze coating, or further, prevent it from functioning completely and cause the hazing on the inner surface of the front cover to gradually increase. Similar to the case of systems where additives are introduced into the polymer / resin material during manufacturing, the deposition of the curing byproducts is reduced, or the anti-haze function is prevented thereby, which again causes the hazing on the inner surface of the front cover to gradually increase. Also, it has been identified that some of the adhesion promoters used to assist the adhesion of the silicone adhesive, especially those that are volatile, may also have an adverse effect on the function of the anti-haze coating.

[0014] Therefore, the condensation-curing adhesive is one of the most preferably suitable adhesives for sealing the front lens pre-coated with the AHC coating to the lamp body, but it results in the deposition of the curing byproducts and residual crosslinking agent on the surface of the anti-haze coating, or on the surface, the combined use of these materials becomes a problem due to the hazing caused as a result of the deposition of the condensation-curing byproducts.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0015] The disclosure herein aims to provide a suitable alternative condensation-curable SMP-based adhesive composition that, upon curing, can neither minimize nor prevent the function of the anti-haze treated material surface.

MEANS FOR SOLVING THE PROBLEM

[0016] In this specification, a two-component condensation-curing silyl-modified polymer (SMP) adhesive composition comprising a base part, i.e., part A, and a catalyst package, i.e., part B, wherein the base part, i.e., part A, (a) a silyl-modified organic polymer having two or more (R) m (Y 1 ) 3-m -Si groups [wherein each R is a hydroxyl group or a hydrolyzable group, and each Y 1 is an alkyl group having 1 to 8 carbon atoms, and m is 1, 2, or 3], which is an organic polymer selected from polyethers, hydrocarbon polymers, acrylate polymers, polyesters, polyurethanes, and polyureas and (b) a reinforcing filler, and the catalyst package, i.e., part B, comprises (i) a condensation-curing catalyst, (ii) a crosslinking agent, wherein (iia) the structure R 6 j Si(OR 5 ) 4-j [wherein each R 5 may be the same or different and is an alkyl group having 2 or more carbon atoms, j is 1 or 0, R 6 is a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 2 or more carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a silicon-bonded organic group selected from any one of the foregoing, wherein one or more hydrogen atoms bonded to carbon are substituted by halogen atoms, or an organic group having an epoxy group, a glycidyl group, an acyl group, a carboxyl group, an ester group, an amino group, an amide group, a (meth)acrylic group, a mercapto group, or an isocyanate group] of silane, (iib) the structure R 7 Si(OMe)3 [wherein R 7 is R 6Silane, provided that the molecular weight is 190 or more, (iic) structure (R’O)3Si(CH2) n N(H)-(CH2) z NH2 [wherein each R’ may be the same or different and is an alkyl group having 1 to 10 carbon atoms, n is 2 to 10, and z is 2 to 10] of silane, or (iid) structure (R 4 O) r (Y 2 ) 3-r -Si(CH2) x -((NHCH2CH2) t -Q(CH2) x ) w -Si(OR 4 ) r (Y 2 ) 3-r [wherein R 4 is a C 1~10 alkyl group, Y 2 is an alkyl group having 1 to 8 carbon atoms, Q is a chemical group containing a heteroatom having a lone pair, each x is an integer of 1 to 6, t is 0 or 1, each r is independently 1, 2, or 3, and w is 0 or 1] of a two-legged silane, or a mixture of two or more of (iie), (iia), (iib), (iic), and (iid), A crosslinking agent selected from the group consisting of, and optionally, (iii) A silyl-modified organic polymer (a) having two or more (R) m (Y 1 ) 3-m -Si groups in one molecule, and / or (iv) A filler, A two-component condensation-curing silyl-modified polymer-based adhesive composition containing is provided.

[0017] Also provided is a lamp having a lamp body that defines a lamp chamber containing a light source and having a front opening, a front lens provided to fit and engage with the front opening, the front lens having an inner surface and an outer surface, the inner surface further defining the lamp chamber, the inner surface being coated with an anti-haze coating, and the front lens being adhered to the lamp chamber by a cured adhesive made from the composition described hereinabove.

[0018] Furthermore, provided is a method for manufacturing the aforementioned lamp, the method including: a step of preparing a lamp body having a front opening and a front lens, the front lens having at least an inner surface treated with an anti-haze coating; a step of forming a joint between the front lens and the front opening of the lamp body by engaging the front lens with the front opening of the lamp body; and a step of sealing the joint between the front lens and the lamp body with the aforementioned adhesive, the step of sealing including mixing part A and part B of the composition together to form a mixture, applying the mixture to the joint between the front lens and the lamp body, and causing the composition to cure, i.e., sealing by curing the composition.

[0019] Also provided herein is the use of the adhesive composition described herein as an adhesive for adhering a front lens of a lamp, treated with an anti-haze coating, to a lamp body, and at the same time minimizing or preventing the generation of chemical species that inhibit the function of the anti-haze coating.

[0020] As used herein, the concept of "comprising" is used in its broadest sense and means the concepts of "include" and "consist of", and encompasses these.

[0021] For the purposes of this application, "substituted" means that one or more hydrogen atoms in a hydrocarbon group are replaced by another substituent. Examples of such substituents include halogen atoms such as chlorine, fluorine, bromine, and iodine; halogen atom-containing groups such as chloromethyl group, perfluorobutyl group, trifluoroethyl group, and nonafluorohexyl group; oxygen atom; oxygen atom-containing groups such as (meth)acrylic group and carboxyl group; nitrogen atom; nitrogen atom-containing groups such as amino functional group, amide functional group, and cyano functional group; sulfur atom; and sulfur atom-containing groups such as mercapto group, but are not limited thereto.

[0022] The base component is a silyl-modified organic polymer having (a) two or more (R) m (Y 1 ) 3-m -Si groups [wherein each R is a hydroxyl group or a hydrolyzable group, each Y 1 is an alkyl group having 1 to 8 carbon atoms, and m is 1, 2, or 3], and includes an organic polymer selected from polyethers, hydrocarbon polymers, acrylate polymers, polyurethanes, and polyureas.

[0023] (R) m (Y 1 ) 3-m -Si groups may be bonded to the organic polymer backbone via any suitable linking group, or may be directly bonded as appropriate. For example, in the case of a silyl-modified polyether polymer, (R) m (Y 1 ) 3-m -Si groups may be end groups bonded to the polyether polymer backbone via the following. (R) m (Y 1 ) 3-m -Si-D-[NH-C(=O)] k - wherein R, Y 1 , and m are as described above, and D is a divalent C 2-6 alkylene group, or C 2-4It is an alkylene group, or an ethylene group or a propylene group, and k is 1 or 0. Therefore, the silyl-modified polyether can be represented as follows. (R) m (Y 1 ) 3-m -Si-D-[NH-C(=O)] k -O[CH(CH3)-CH2-O] u -[C(=O)-NH] k -D-Si(Y 1 ) 3-m (R) m Here, in the above example, the polyether repeating group is, for example, an oxypropylene group [CH(CH3)-CH2-O].

[0024] (R) m (Y 1 ) 3-m Each substituent R in the -Si group may independently be a hydroxyl group or a hydrolyzable group. The hydrolyzable group may be an acyloxy group (for example, an acetoxy group, an octanoyloxy group, and a benzoyloxy group); a ketoximino group (for example, a dimethylketoximo group and an isobutylketoximino group); an alkoxy group (for example, a methoxy group, an ethoxy group, and a propoxy group), and an alkenyloxy group (for example, an isopropenyloxy group and a 1-ethyl-2-methylvinyloxy group). However, each R is preferably an OH group, or an alkoxy group having 1 to 10 carbon atoms, or an OH group, or an alkoxy group having 1 to 6 carbon atoms, or an OH group, a methoxy group, or an ethoxy group. Substituent Y 1 is an alkyl group having 1 to 8 carbon atoms, or having 1 to 6 carbon atoms, or having 1 to 4 carbon atoms. Therefore, when R is an OH or a hydrolyzable group and the hydrolyzable group is an alkoxy group, (R) m (Y 1 ) 3-m -Si group is -(Y 1 )SiOH2, -(Y 1 )2SiOH-, -Y 1 Si(OR b)2-, -Si(OR b )3, -(Y 1 )2SiOR b may be selected from, R b is an alkyl group having 1 to 8 carbon atoms. Typically, the silyl-modified organic polymer has an organic main chain with terminal curable silyl groups.

[0025] One preferred type of polymer main chain is an acrylate polymer main chain. An acrylate polymer is an addition polymerization polymer of acrylate and / or methacrylate ester monomers, and contains 50% by weight or more (i.e., 50% to 100% by weight) of monomer units in the acrylate polymer. Examples of acrylate ester monomers are n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, ethyl acrylate, methyl acrylate, n-hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate. Examples of methacrylate ester monomers are n-butyl methacrylate, isobutyl methacrylate, methyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate. The glass transition temperature (Tg) of the acrylate polymer is preferably below ambient temperature, and since the acrylate polymer forms a polymer with a lower Tg, it is generally more preferred than methacrylate. Polybutyl acrylate is particularly preferred. The acrylate polymer may contain only a small amount of other monomers such as styrene, acrylonitrile, or acrylamide. The acrylate can be polymerized by various methods such as conventional radical polymerization or living radical polymerization (such as atom transfer radical polymerization), reversible addition fragmentation chain transfer polymerization, or anionic polymerization (e.g., living anionic polymerization).

[0026] In one alternative, the alkoxysilyl-terminated organic polymer is a polyether as described above. The polymer main chain has the above structure, [CH(CH3)-CH2-O] u Exemplified as such, such polyethers may contain various repeating oxyalkylene units exemplified by the average formula (-C p H 2p -O-) y [wherein p is an integer from 2 to 4 and y is 4 or more, i.e., an integer of 4 or more]. The number average molecular weight (Mn) of each polyether may be in the range of about 300 to about 10,000, determined by ASTM D5296-05 and calculable as polystyrene molecular weight equivalent. Further, the oxyalkylene units are not necessarily the same throughout the polyoxyalkylene and may be different for each unit. The polyoxyalkylene may contain, for example, oxyethylene units (-C2H4-O-), oxypropylene units (-C3H6-O-), or oxybutylene units (-C4H8-O-), or combinations thereof. Preferably, the polyoxyalkylene polymer main chain consists essentially of oxyethylene units or oxypropylene units. Other polyoxyalkylenes include, for example, the structure, -[-R e -O-(-R f -O-) h -Pn-CR g 2-Pn-O-(-R f -O-) q1 -R e - [wherein Pn is a 1,4-phenylene group, each R e is the same or different and is a divalent hydrocarbon group having 2 to 8 carbon atoms, each R f is the same or different and is an ethylene group or a propylene group, each R g is the same or different and is a hydrogen atom or a methyl group, and each of the subscripts h and q1 is a positive integer in the range of 3 to 30] may be included.

[0027] One preferred type of polyether has the formula (-C p H 2pThere is a polyoxyalkylene polymer containing a repeating oxyalkylene unit of [-O-)[wherein p is an integer of 2 to 4]]. The polyoxyalkylene polymer usually has a terminal hydroxyl group and can be easily modified with a moisture-curable silyl group, for example, by reacting with an excess of an alkyltrialkoxysilane to introduce a terminal alkyldialkoxysilyl group as described above. Alternatively, the polymerization may occur by a hydrosilylation-type process. The properties of polyoxyalkylene consisting entirely or mainly of oxypropylene units are suitable for many adhesive applications.

[0028] Examples of silyl-modified hydrocarbon polymers include silyl-modified polyisobutylene. Silyl-modified polyisobutylene may contain, for example, a curable silyl group derived from a silyl-substituted alkyl acrylate or methacrylate monomer (such as alkoxydialkylsilylpropyl methacrylate, dialkoxyalkylsilylpropyl methacrylate, or trialkoxysilylpropyl methacrylate), which can react with polyisobutylene.

[0029] Typically, the SMP polymer is present in the base composition in an amount of 30 to 80% by weight of the base composition, or 35 to 65% by weight of the base composition, or 40 to 60% by weight of the base composition.

[0030] The base component reinforcing filler (b) may contain one or more finely divided reinforcing fillers such as precipitated calcium carbonate, fumed silica, and / or precipitated silica, including, for example, rice husk ash. Typically, the surface area of the reinforcing filler (b) is measured by the BET method in accordance with ISO 9277:2010. In the case of precipitated calcium carbonate, it is 15 m 2 / g or more, or 15 to 50 m 2 / g, or 15 to 25 m 2 / g. The silica reinforcing filler is 50 m 2It has a typical surface area of / g or more. In one embodiment, the reinforcing filler (b) is precipitated calcium carbonate, precipitated silica and / or fumed silica, or is precipitated calcium carbonate. In the case of high surface area fumed silica and / or high surface area precipitated silica, these have a surface area of 100 to 400 m 2 / g as measured by the BET method in accordance with ISO 9277:2010, or can be selected for use with a surface area of 100 to 300 m 2 / g as measured by the BET method in accordance with ISO 9277:2010. Typically, the reinforcing filler is present in the base composition in an amount of 20 to 70% by weight of the base composition, or 35 to 65% by weight of the base composition, or 40 to 60% by weight of the base composition.

[0031] The reinforcing filler (b) can be hydrophobically treated with, for example, one or more fatty acids, such as stearic acid, or fatty acid esters such as stearate, or organosilanes, polydiorganosiloxanes, or organosilazanes hexaalkyldisilazane, or short-chain siloxane diols, to make the filler hydrophobic, and thereby make it easier to handle and obtain a homogeneous mixture with other adhesive components. The surface treatment of the filler facilitates wetting by the siloxane polymer (a) of the base component. These surface-modified fillers do not aggregate and can be homogeneously incorporated into the silicone polymer (a) of the base component. This improves the mechanical properties of the uncured composition at room temperature. The filler may be pretreated or treated in situ when mixed with the polymer (a).

[0032] As described above, the catalyst package of the composition of two components includes the catalyst package, i.e., part B, and part B is (i) a condensation curing catalyst, and (ii) a crosslinking agent, where (iia) the structure R 6 j Si(OR 5 ) 4-j [wherein each R 5may be the same or different and is an alkyl group having 2 or more carbon atoms, j is 1 or 0, R 6 is a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 2 or more carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a silicon-bonded organic group selected from any one of the foregoing, in which one or more hydrogen atoms bonded to carbon are substituted by halogen atoms, or an organic group having an epoxy group, a glycidyl group, an acyl group, a carboxyl group, an ester group, an amino group, an amide group, a (meth)acrylic group, a mercapto group, or an isocyanate group] of silane, (iib) structure R 7 Si(OMe)3 [wherein R 7 is R 6 of silane, provided that the molecular weight is 190 or more, (iic) (R’O)3Si(CH2) n N(H)-(CH2) z NH2 [wherein each R’ may be the same or different and is an alkyl group having 1 to 10 carbon atoms, n is 2 to 10, and z is 2 to 10] of silane, (iid) structure (R 4 O) r (Y 2 ) 3-r -Si(CH2) x -((NHCH2CH2) t -Q(CH2) x ) w -Si(OR 4 ) r (Y 2 ) 3-r [wherein R 4 is a C1-10 alkyl group, Y 2 is an alkyl group having 1 to 8 carbon atoms, Q is a chemical group containing a heteroatom having a lone pair of electrons, each x is an integer from 1 to 6, t is 0 or 1, each r is independently 1, 2, or 3, w is 0 or 1] of the bipodal silane, or (iie) A mixture of two or more of (iia), (iib), (iic), and (iid), selected from the group consisting of crosslinking agents, and optionally, (iii) Two or more (R) in one molecule m (Y 1 ) 3-m -Si group-containing silyl-modified organic polymer (a), and / or (iv) a filler.

[0033] The condensation curing catalyst (i) may be any suitable tin-based condensation catalyst (i) suitable for catalyzing the curing of the entire composition after mixing the base component and the catalyst package component together. Examples include tin triflate, organotin metal catalysts such as triethyltin tartrate, tin octoate, tin oleate, tin naphthenate, butyltin tri-2-ethylhexoate, tin butyrate, carbomethoxyphenyltin trisverate, isobutyltin tricerate, and diorganotin salts, especially diorganotin dicarboxylate compounds such as dibutyltin dilaurate, dimethyltin dibutyrate, dibutyltin dimethoxide, dibutyltin diacetate, dimethyltin bisneodecanoate, dibutyltin dibenzoate, stannous octoate, dibutyltin bis(2,4-pentanedionate, dimethyltin bisneodecanoate (DMTDN), and dibutyltin dioctoate.

[0034] Alternatively, the condensation catalyst (i) may be a titanium-based catalyst or a zirconium-based catalyst. The catalyst selected for inclusion in a particular silicone sealant composition varies depending on the required curing rate. Titanate-based catalysts and / or zirconate-based catalysts have the general formula Ti[OR 9 4 or Zr[OR 9 4 [wherein each R 9may be the same or different and represents a monovalent, primary, secondary, or tertiary aliphatic hydrocarbon group that may be linear or branched and have 1 to 10 carbon atoms. Optionally, the titanate may contain a partially unsaturated group. Note that R 9 Preferred examples of include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tertiary butyl group, and a branched secondary alkyl group, such as a 2,4-dimethyl-3-pentyl group, but are not limited thereto. Each R 9 When are the same, preferably, R 9 is an isopropyl group, a branched secondary alkyl group, or a tertiary alkyl group, particularly a tertiary butyl group. Suitable examples include, for example, tetra-n-butyl titanate, tetra-t-butyl titanate, tetra-t-butoxy titanate, tetraisopropoxy titanate, and diisopropoxydiethylacetoacetate titanate (and equivalents of zirconate). Alternatively, the titanate / zirconate may be chelated. Chelation may be by any suitable chelating agent, such as alkyl acetylacetonate, for example methyl or ethyl acetylacetonate. Alternatively, the titanate may be a monoalkoxy titanate that provides three chelating agents, such as 2-propanolato, tris isooctadecanoato titanate.

[0035] The catalyst package also contains a crosslinking agent (ii). The crosslinking agent (ii) has a structure R 6 j Si(OR 5 ) 4-j [wherein each R 5 may be the same or different and is an alkyl group having 2 or more carbon atoms, or having 2 to 20 carbon atoms, or having 2 to 10 carbon atoms, or having 2 to 6 carbon atoms] and may be selected from silanes (iia). The value of "j" is 0 or 1. Each R 5 groups may be the same or different, but two or more R 5 groups are the same, or three or more R 5The groups are the same, or when j is 0, all Rs 5 The groups are preferably the same. Therefore, specific examples of the crosslinking agent (iia) when j is zero include tetraethyl orthosilicate, tetrapropyl orthosilicate, tetra(n-)butyl orthosilicate, and tetra(t-)butyl orthosilicate.

[0036] When j is 1, an R 6 group is present. R 6 is a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 2 or more carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a silicon-bonded organic group selected from any one of the foregoing, wherein one or more hydrogen atoms bonded to carbon are substituted by a halogen atom, or an organic group having an epoxy group, a glycidyl group, an acyl group, a carboxyl group, an ester group, an amino group, an amide group, a (meth)acrylic group, a mercapto group, an isocyanurate group, or an isocyanate group. R 6 Suitable unsubstituted monovalent hydrocarbon groups as R include alkyl groups such as an ethyl group, a propyl group, and other alkyl groups, and alkenyl groups, and suitable cycloalkyl groups include a cyclopentane group and a cyclohexane group. R 6 Suitable substituents for or as it include, for example, a 3-hydroxypropyl group, a 3-(2-hydroxyethoxy)alkyl group, a halopropyl group, a 3-mercaptopropyl group, a trifluoroalkyl group such as a 3,3,3-trifluoropropyl group, a 2,3-epoxypropyl group, a 3,4-epoxybutyl group, a 4,5-epoxypentyl group, a 2-glycidoxyethyl group, a 3-glycidoxypropyl group, a 4-glycidoxybutyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)alkyl group, an aminopropyl group, an N-methylaminopropyl group, an N-butylaminopropyl group, an N,N-dibutylaminopropyl group, a 3-(2-aminoethoxy)propyl group, a methacryloxyalkyl group, an acryloxyalkyl group, a carboxyalkyl group such as a 3-carboxypropyl group, a 10-carboxydecyl group.

[0037] Specific examples of suitable crosslinking agent (IIa) include ethyltriethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, methyltris(isopropenoxy)silane or vinyltris(isopropenoxy)silane, 3-hydroxypropyltriethoxysilane, 3-(2-hydroxyethoxy)ethyltriethoxysilane, chloropropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2,3-epoxypropyltriethoxysilane, 3,4-epoxybutyltriethoxysilane, 4,5-epoxypentyltriethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(3,4-epoxycyclohexyl)ethyltriethoxysilane, aminopropyltriethoxysilane, N-methylaminopropyltriethoxysilane, N-butylaminopropyltriethoxysilane, N,N-dibutylaminopropyltriethoxysilane, 3-(2-aminoethoxy)propyltriethoxysilane, methacryloxypropyltriethoxysilane, tris(3-triethoxysilylpropyl)isocyanurate, acryloxypropyltriethoxysilane, 3-carboxypropyltriethoxysilane, and 10-carboxydecyltriethoxysilane, but are not limited thereto.

[0038] The crosslinking agent (II) may further or alternatively contain a compound of structure (IIb) R 7 Si(OMe)3 [wherein R 7 is R 6 ), provided that the molecular weight of the silane (IIb) is 190 or more.

[0039] Therefore, R 7It may also be a silicon-bonded organic group selected from the following list, provided that its molecular weight is 190 or more. Therefore, this is a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 5 or more carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a silicon-bonded organic group selected from any one of the foregoing, wherein one or more hydrogen atoms bonded to carbon are substituted by a halogen atom, or an organic group having an epoxy group, a glycidyl group, an acyl group, a carboxyl group, an ester group, an amino group, an amide group, a (meth)acryl group, a mercapto group, or an isocyanate group. R 6 Suitable unsubstituted monovalent hydrocarbon groups include alkyl groups having 5 or more carbon atoms, such as pentyl group, hexyl group, and other longer-chain alkyl groups, and alkenyl groups having 5 or more carbon atoms. Examples of the cycloalkyl group include cyclopentane group and cyclohexane group. R 6 Suitable substituents for or as it include, for example, 3-(2-hydroxyethoxy)alkyl group, halopropyl group, 3-mercaptopropyl group, trifluoroalkyl group, such as 3,3,3-trifluoropropyl group, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group, 2-(3,4-epoxycyclohexyl)ethyl group, 3-(3,4-epoxycyclohexyl)alkyl group, aminopropyl group, N-methylaminopropyl group, N-butylaminopropyl group, N,N-dibutylaminopropyl group, 3-(2-aminoethoxy)propyl group, isocyanurate group, methacryloxyalkyl group, acryloxyalkyl group, carboxyalkyl group, such as 3-carboxypropyl group, 10-carboxydecyl group.

[0040] Specific examples of suitable crosslinking agents (IIb) include, but are not limited to, pentyltrimethoxysilane, hexyltrimethoxysilane, hexenyltrimethoxysilane, phenyltrimethoxysilane, 3-(2-hydroxyethoxy)ethyltrimethoxysilane, chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 2,3-epoxypropyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 4,5-epoxypentyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 4-glycidoxybutyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, N,N-dibutylaminopropyltrimethoxysilane, 3-(2-aminoethoxy)propyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, 3-carboxypropyltrimethoxysilane, and 10-carboxydecyltrimethoxysilane.

[0041] The crosslinking agent (II) has the structure (IIc) (R’O)3Si(CH2) n N(H)-(CH2) z NH2 The compound of [[wherein each R' may be the same or different and is an alkyl group having 1 to 10 carbon atoms, n is 2 to 10, and z is 2 to 10]] may be further or alternatively included. Each R' may be the same or different and is an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, or a methyl group or an ethyl group. In one alternative, two or more R' groups are the same, or all R' groups are the same. When two or more R' groups are the same, or all R' groups are the same, they are preferably a methyl group or an ethyl group. In one alternative, there may be n -CH2- groups, where n is 2 to 10. In one alternative, n may be 2 to 6. In another alternative, n may be 2 to 5. In still further alternatives, n may be 2 or 3, or n is 3. There may be z -CH2- groups, where z is 2 to 10. In one alternative, z may be 2 to 6. In another alternative, z may be 2 to 5. In still further alternatives, z may be 2 or 3, or z is 2. Specific examples include, but are not limited to, (ethylenediaminepropyl)trimethoxysilane and (ethylenediaminepropyl)triethoxysilane.

[0042] The crosslinking agent (ii) has the structure (R 4 O) r (Y 2 ) 3-r -Si(CH2) x -((NHCH2CH2) t -Q(CH2) x ) w -Si(OR 4 ) r (Y 2 ) 3-r [wherein, R 4 is a C 1~10 alkyl group, and Y 2 is an alkyl group having 1 to 8 carbon atoms, Q is a chemical group containing a heteroatom with a lone pair of electrons, each x is an integer from 1 to 6, t is 0 or 1, each r is independently 1, 2, or 3, and w is 0 or 1], and the two-legged silane (iid) may be further or alternatively included.

[0043] Examples of the two-legged silane (iid) include, when w = 0, bis(trimethoxysilyl)hexane and bis(trimethoxysilyl)hexane.

[0044] When w = 1, the two-legged silane (iid) of the catalyst package has the following formula (R 4 O) r (Y 2 ) 3-r -Si(CH2) x -(NHCH2CH2) t -Q(CH2) x -Si(OR 4 ) r (Y 2 ) 3-r [wherein R 4 is a C 1-10 alkyl group, Y 2 is an alkyl group having 1 to 8 carbon atoms, Q is a chemical group having a heteroatom with a lone pair of electrons, or an amine or urea, each x is an integer from 1 to 6, t is 0 or 1, each r is independently 1, 2 or 3, or 2 or 3, and in a further alternative example, r = 3] can be defined by.

[0045] In one alternative example, Q is a secondary amine and each x is from 2 to 4.

[0046] Examples of the two-legged silane (iid) include, when w = 1, Bis(trialkoxysilylalkyl)amine, bis(dialkoxysilylalkyl)amine, bis(trialkoxysilylalkyl)N-alkylamine, bis(dialkoxysilylalkyl)N-alkylamine, bis(trialkoxysilylalkyl)urea, and bis(dialkoxysilylalkyl)urea are mentioned.

[0047] As specific preferred examples, for example, bis(3-trimethoxysilylpropyl)amine, Bis(3-triethoxysilylpropyl)amine, bis(4-trimethoxysilylbutyl)amine, bis(4-triethoxysilylbutyl)amine, bis(3-trimethoxysilylpropyl)N-methylamine, bis(3-triethoxysilylpropyl)N-methylamine, bis(4-trimethoxysilylbutyl)N-methylamine, bis(4-triethoxysilylbutyl)N-methylamine, bis(3-trimethoxysilylpropyl)urea, bis(3-triethoxysilylpropyl)urea, bis(4-trimethoxysilylbutyl)urea, bis(4-triethoxysilylbutyl)urea, bis(3-dimethoxymethylsilylpropyl)amine, bis(3-diethoxymethylsilylpropyl)amine, bis(4-dimethoxymethylsilylbutyl)amine, bis(4-diethoxymethylsilylbutyl)amine, bis(3-dimethoxymethylsilylpropyl)N-methylamine, bis(3-diethoxymethylsilylpropyl)N-methylamine, bis(4-dimethoxymethylsilylbutyl)N-methylamine, bis(4-diethoxymethylsilylbutyl)N-methylamine, bis(3-dimethoxymethylsilylpropyl)urea, bis(3-diethoxymethylsilylpropyl)urea, bis(4-dimethoxymethylsilylbutyl)urea, bis(4-diethoxymethylsilylbutyl)urea, bis(3-dimethoxyethylsilylpropyl)amine, bis(3-diethoxyethylsilylpropyl)amine, bis(4-dimethoxyethylsilylbutyl)amine, bis(4-diethoxyethylsilylbutyl)amine, bis(3-dimethoxyethylsilylpropyl)N-methylamine, bis(3-diethoxyethylsilylpropyl)N-methylamine, bis(4-dimethoxyethylsilylbutyl)N-methylamine, bis(4-diethoxyethylsilylbutyl)N-methylamine, bis(3-dimethoxyethylsilylpropyl)urea, bis(3-diethoxyethylsilylpropyl)urea, bis(4-dimethoxyethylsilylbutyl)urea, and / or bis(4-diethoxyethylsilylbutyl)urea may be mentioned.

[0048] In still further alternative examples, the two-legged silane (iid) is of the following formula, (R 4O)3-Si(CH2) x -(NHCH2CH2) t -NH(CH2) x -Si(OR 4 )3 In this case, the bifurcated silane may be selected from bis(trialkoxysilylalkyl)amines such as bis(3-tripropoxysilylpropyl)amine, bis(3-methyldiethoxysilylpropyl)amine, bis(3-methyldimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine, or may be bis(trialkoxysilylalkyl)alkylenediamines such as N,N-bis((3-trimethoxysilyl)propyl]ethylenediamine.

[0049] The crosslinking agent may alternatively be a mixture of two or more of (iia), (iib), (iic), and (iid). In one embodiment, the crosslinking agent is a crosslinking agent having the (iic) structure alone or in combination with a crosslinking agent of type (iid).

[0050] Optionally, the catalyst package may also (iii) a silyl-modified organic polymer having two or more (R) m (Y 1 ) 3-m -Si groups in one molecule, and / or (iv) a filler, and may include one or more of these. The optionally present silyl-modified organic polymer (iii) having two or more (R) m (Y 1 ) 3-m -Si groups in one molecule has the same definition as above for the silyl-modified organic polymer (a) and may in fact be an additional amount of the same polymer as (a) above, but is not limited thereto.

[0051] The filler (iv) in the catalyst part may be the reinforcing filler according to (b) above, or may be a non-reinforcing filler or a mixture thereof.

[0052] Suitable non-reinforcing fillers may include, for example, crushed quartz, crushed calcium carbonate, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide, and carbon black, and talc may be present in the composition. Other non-reinforcing fillers that can be used alone or in addition to the above include aluminite, calcium sulfate (anhydrite), gypsum, calcium sulfate, magnesium carbonate, clay such as kaolin, aluminum trihydroxide, magnesium hydroxide (hydrotalcite), graphite, copper carbonate such as malachite, nickel carbonate such as zarachite, barium carbonate such as witherite, and / or strontium carbonate such as strontianite.

[0053] Silicates from the group consisting of aluminum oxide, cancrinite group; pectolite group; aluminosilicates; cyclic silicates; chain silicates; and layered silicates are included. The cancrinite group includes, but is not limited to, silicate minerals such as forsterite and Mg2SiO4. The pectolite group includes, but is not limited to, ground silicate minerals such as red pectolite; Mg3Al2Si3O 12 ; green pectolite; and Ca2Al2Si3O 12 and the like. Aluminosilicates include, but are not limited to, ground silicate minerals such as sillimanite; Al2SiO5; mullite; 3Al2O3.2SiO2; kyanite; and Al2SiO5. The cyclic silicate group includes, but is not limited to, silicate ores such as cordierite and Al3(Mg, Fe)2[Si4AlO 18 . The chain silicate group includes, but is not limited to, ground silicate minerals such as wollastonite and Ca[SiO3].

[0054] Layered silicates are mica; K2AI 14 [Si6Al2O 20 (OH)4; chlorite; Al4[Si8O 20 (OH)4; talc, Mg6[Si8O 20(OH)4; serpentine, such as asbestos; kaolinite; Al4[Si4O 10 (OH)8; and silicate minerals such as vermiculite, but not limited thereto.

[0055] The non-reinforcing filler can also be surface-treated using a treatment agent similar to those discussed for the above-mentioned reinforcing fillers to make it hydrophobic.

[0056] In one embodiment, the optional filler (iv) in part B of the composition herein is ground calcium carbonate, precipitated calcium carbonate, precipitated silica, and / or fumed silica. The content of each component in the catalyst package depends at least in part on the predetermined weight ratio of the two parts when mixed immediately before use. Typically, the base component composition and the catalyst package composition can be mixed at a predetermined weight ratio of 15:1 to 1:1, or 15:1 to 2:1, or when the two parts are mixed together, 12:1 to 2:1. When the intended mixing weight ratio of the base component to the catalyst package is 12:1 or more, i.e., 15:1 to 12:1, the contents of the catalyst package may be only component (i) (condensing catalyst) and (ii) (crosslinking agent). In this case, the crosslinking agent is present in an amount of about 60 to 80% by weight of the catalyst package, and the catalyst is present in an amount of 20 to 40% by weight of the total catalyst composition accordingly, provided that no additive is present. However, in a situation where the base composition and the catalyst package are mixed at a weight ratio approaching 1:1, most of the catalyst package consists of component (iii) polymer (a) and filler (iv) and a small amount of components (i) and (ii) in view of the same final composition. In such a case, the condensing catalyst is present in an amount of 0.01 to 20% by weight, or 0.1 to 5% by weight, of the catalyst package, and the crosslinking agent (ii) is present in an amount of 2 to 30% by weight of the catalyst composition, but generally 2 to 15% by weight, or 4 to 11% by weight, of the catalyst composition.

[0057] Other additives may be used as necessary. These include pigments, rheology modifiers, plasticizers, antioxidants, heat stabilizers, flame retardants, UV stabilizers, water scavengers (typically the same compounds used as crosslinking agents or silazanes), curing modifiers, electrically conductive fillers, thermally conductive fillers, and fungicides and / or biocides, and co-catalysts for promoting the curing of the composition, such as metal salts of carboxylic acids and amines. It is understood that some of the additives may be listed in the list of multiple additives. In that case, such additives have the ability to function in all the different applications mentioned.

[0058] Pigments are utilized as necessary to color the composition. Any suitable pigment can be used as long as it is compatible with the composition. In two-component compositions, pigments and / or colored (non-white) fillers, such as carbon black, can be utilized in the catalyst package to color the final adhesive product. When present, carbon black functions as both a non-reinforcing filler and a colorant and is present in the range of 1 to 30% by weight of the catalyst package composition, or 1 to 20% by weight of the catalyst package composition, or 5 to 20% by weight of the catalyst package composition, or 7.5 to 20% by weight of the catalyst composition.

[0059] Rheology modifiers that can be incorporated into the moisture-curable composition according to the present invention include silicone organic copolymers, such as those described in European Patent No. 0802233 based on polyols of polyethers or polyesters; nonionic surfactants selected from the group consisting of polyethylene glycol, polypropylene glycol, ethoxylated castor oil, ethoxylated oleic acid, alkylphenol ethoxylate, copolymers or ethylene oxide and propylene oxide, and silicone polyether copolymers; and silicone glycols. For some systems, these rheology modifiers, particularly copolymers of ethylene oxide and propylene oxide, and silicone polyether copolymers, can enhance the adhesion to substrates, particularly plastic substrates.

[0060] Plasticizers are often used in silyl-modified organic polymer-based compositions. Considering the fact that the polymer backbone is substantially organic (i.e., does not contain Si-O-Si bonds in the polymer backbone), plasticizers are generally selected from those suitable for plasticizing polymer (a) and case (iii) when present. Examples include hydroxyl-terminated polypropylene ether, hydroxyl-terminated polyethylene ether, and hydroxyl-terminated polypropylene / polyethylene ether copolymer. Also included are alkoxy-terminated polypropylene ether, alkoxy-terminated polyethylene ether, and alkoxy-terminated polypropylene / polyethylene ether copolymer. A commercially available hydroxyl-terminated polypropylene ether is sold under the trade name VORANOL by the Dow Chemical Company.

[0061] If desired, any suitable antioxidant can be utilized. Examples include ethylenebis(oxyethylene)bis(3-tert-butyl-4-hydroxy-5(methylhydrocinnamate), 36443-68-2; tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, 6683-19-8; octadecyl[3,5-di-tert-butyl-4-hydroxyhydroxycinnamate, 2082-79-3; N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydroxycinnamamide), 23128-74-7; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-9 branched alkyl ester, 125643-61-0; the reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene, 68411-46-1; for example, antioxidants sold under the name Irganox® by BASF can be mentioned.

[0062] If necessary, biocides can be further used in the composition. It should be noted that the term "biocide" includes bactericides, fungicides, algicides, etc. Suitable examples of useful biocides that can be used in the compositions described herein include, for example:

[0063] carbamates, such as methyl-N-benzimidazol-2-ylcarbamate (carbendazim) and other suitable carbamates, 10,10'-oxybisphenoxazine, 2-(4-thiazolyl)-benzimidazole, N-(fluorodichloromethylthio)phthalimide, diiodomethyl p-tolylsulfone, 2,6-di(tert-butyl)-p-cresol when appropriate in combination with ultraviolet stabilizers, 3-iodo-2-propynyl butylcarbamate (IPBC), zinc 2-pyridinethiol-1-oxide, triazolyl compounds and isothiazolinones, such as 4,5-dichloro-2-(n-octyl)-4-isothiazolin-3-one (DCOIT), 2-(n-octyl)4-isothiazolin-3-one (OIT), and n-butyl-1,2-benzisothiazolin-3-one (BBIT), etc.; other biocides include, for example, zinc pyrithione, 1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-ylmethyl)pentan-3-ol and / or 1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole.

[0064] Preferably, the fungicide and / or biocide may be present in an amount of 0 to 0.3% by weight of the composition and, as described in European Patent No. 2106418, may be present in encapsulated form if required.

[0065] Examples of heat stabilizers can be cited, and examples of heat stabilizers include metal compounds, such as red iron oxide, yellow iron oxide, ferric hydroxide, cerium oxide, cerium hydroxide, lanthanum oxide, copper phthalocyanine, aluminum hydroxide, fumed titanium dioxide, iron naphthenate, cerium naphthenate, cerium dimethylpolysilanolate, and acetylacetone salts of metals selected from copper, zinc, aluminum, iron, cerium, zirconium, titanium, etc.

[0066] Examples of flame retardants can include, for example, carbon black, aluminum hydroxide hydrate, and silicates (e.g., wollastonite), platinum, and platinum compounds.

[0067] Examples of UV stabilizers can include, for example, benzotriazole UV absorbers and / or hindered amine light stabilizers (HALS), such as product items of TINUVIN (registered trademark) manufactured by Ciba Specialty Chemicals Inc.

[0068] Examples of electrically conductive fillers can include carbon black, metal particles such as silver particles, any suitable electrically conductive metal oxide filler, for example, titanium oxide powder whose surface is treated with tin and / or antimony, potassium titanate powder whose surface is treated with tin and / or antimony, tin oxide whose surface is treated with antimony, and zinc oxide whose surface is treated with aluminum.

[0069] Examples of heat conductive fillers can include metal particles, such as powders, flakes and colloidal silver, copper, nickel, platinum, gold, aluminum, and titanium, metal oxides, especially aluminum oxide (Al2O3), and beryllium oxide (BeO), magnesium oxide, zinc oxide, zirconium oxide, ceramic fillers, such as tungsten carbide, silicon carbide and aluminum nitride, boron nitride and diamond.

[0070] In the case of a two-part composition, the base component, with the total weight percentage of the base component being 100% by weight, 20 to 80% by weight, or 35 to 65% by weight, of a silyl-modified organic polymer (a), and 20 to 80% by weight, or 35 to 65% by weight, of a reinforcing filler (b), and

[0071] The additives can preferably be introduced into either part A or part B of the composition. For example, plasticizers, antioxidants, UV stabilizers, and / or pigments are most likely to be introduced into part A, but alternatively, they may be present in the part B composition.

[0072] In the two-part composition, the catalyst package, i.e., part B, typically has, with the total weight percentage of the catalyst package being 100% by weight, Based on the weight of the catalyst package, a condensation-curing (e.g., tin) - based catalyst (i) in an amount of 0.5 to 40% by weight, Based on the weight of the catalyst package, a crosslinking agent (ii) in an amount of 1 to 80% by weight, and optionally Based on the weight of the catalyst package, a silyl-modified organic polymer having two or more (R) m (Y 1 ) 3-m -Si groups in one molecule, and / or Based on the weight of the catalyst package, a filler in an amount of 0 to 40% by weight.

[0073] The final composition when part A and part B are mixed together typically has, based on the weight of the combined composition, the following: 18 to 72% by weight, or 35 to 67% by weight, of the SMP polymer (a), and 18 to 63% by weight, or 25 to 50% by weight, of the reinforcing filler (b), and A condensation catalyst (i) in an amount of 0.5 to 5% by weight, A crosslinking agent (ii) in an amount of 1 to 15% by weight, or 2 to 10% by weight, as a basis, and optionally A filler from the catalyst package in an amount of 0 to 40% by weight, and Follows the policy of other optional components as required.

[0074] The composition is preferably a room temperature vulcanizable composition in that it cures at room temperature without heating, but can be accelerated by heating if considered appropriate.

[0075] The composition of part A and part B can be prepared by mixing the components using any suitable mixing device. Other optional additional components can be added to either part A or part B when considered appropriate.

[0076] After mixing, the composition of part A and part B, particularly the composition of part B, can be stored until needed for use under substantially anhydrous conditions, for example, in a sealed container.

[0077] Also provided is a lamp having a lamp body defining a lamp chamber containing a light source and having a front opening, a front lens provided to engage the front opening, the front lens having an inner surface and an outer surface, the inner surface further defining the lamp chamber, the inner surface being coated with an anti-haze coating, and the front lens being adhered to the lamp chamber by a cured adhesive made from a two-part condensation curable SMP-based adhesive composition containing a first part, i.e., part A, where part A is (a) a silyl-modified organic polymer having two or more (R) m (Y 1 ) 3-m -Si groups [where each R is a hydroxyl group or a hydrolyzable group, each Y 1 is an alkyl group having 1 to 8 carbon atoms, and m is 1, 2, or 3], which is an organic polymer selected from polyethers, hydrocarbon polymers, acrylate polymers, polyesters, polyurethanes, and polyureas and (b) a reinforcing filler, and a catalyst package, i.e., part B is (i) a tin-based catalyst, and (ii) a crosslinking agent, where (iia) the structure R6 j Si(OR 5 ) 4-j [wherein each R 5 may be the same or different and is an alkyl group having 2 or more carbon atoms, j is 1 or 0, R 6 is a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 2 or more carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a silicon-bonded organic group selected from any one of the foregoing, in which one or more hydrogen atoms bonded to carbon are substituted by halogen atoms, or an organic group having an epoxy group, a glycidyl group, an acyl group, a carboxyl group, an ester group, an amino group, an amide group, a (meth)acrylic group, a mercapto group, or an isocyanate group] silane, (iib) structure R 7 Si(OMe)3 [wherein R 7 is R 6 however, the molecular weight is 190 or more] silane, (iic) structure (R’O)3Si(CH2) n N(H)-(CH2) z NH2 [wherein each R’ may be the same or different and is an alkyl group having 1 to 10 carbon atoms, n is 2 to 10, and z is 2 to 10] silane, (iid) structure (R 4 O) r (Y 2 ) 3-r -Si(CH2) x -((NHCH2CH2) t -Q(CH2) x ) w -Si(OR 4 ) r (Y 2 ) 3-r [wherein R 4 is a C1-10 alkyl group, Y 2is an alkyl group having 1 to 8 carbon atoms, Q is a chemical group containing a heteroatom having a lone pair of electrons, each x is an integer from 1 to 6, t is 0 or 1, each r is independently 1, 2, or 3, and w is 0 or 1] of a bipodal silane, or (iie) A mixture of two or more of (iia), (iib), (iic), and (iid), selected from the group consisting of, a crosslinking agent, and optionally, (iii) Two or more (R) in one molecule m (Y 1 ) 3-m -Si group-containing silyl-modified organic polymer (a), and / or (iv) A filler, is included.

[0078] The lamp body may be made of any suitable material such as polybutylene terephthalate (PBT), cast aluminum, acrylonitrile-butadiene-styrene (ABS), polypropylene (PP), ethylene-propylene-diene monomer rubber (EPDM), polyphenylene sulfide (PPS), polyether ether ketone (PEEK), low density polyethylene (LDPE), high density polyethylene (HDPE), polyamide (PA), acrylic-styrene-acrylonitrile (ASA), polyether ether ketone (PEEK), and composites thereof. It may also be made of PBT-GF30 (glass fiber-reinforced polybutylene terephthalate), TV40+PP and TV20 / GF10, PBT-MF30, a blend of polybutylene terephthalate and acrylonitrile styrene acrylate (PBT / ASA), and PP+GF20 (glass fiber-reinforced PP).

[0079] The front lens may be made of any suitable material, and specific examples include, but are not limited to, polycarbonate or PMMA.

[0080] The outer surface of the lens can be treated with an anti-scratch coating.

[0081] Also, the above-described method for manufacturing a lamp, which includes a step of preparing a lamp body having a front opening and a front lens, wherein the front lens has at least an inner surface treated with an anti-haze coating; a step of forming a joint portion to the front opening of the lamp body between the front lens by engaging the front lens with the front opening of the lamp body; and a step of sealing the joint portion between the front lens and the lamp body with the above-described adhesive, which includes mixing part A and part B of the composition together to form a mixture, applying the mixture to the joint portion between the front lens and the lamp body, and causing curing of the composition, that is, sealing by curing the composition. The adhesive is a two-component condensation-curable silicone-based adhesive composition, including a first part, that is, part A, and a catalyst package, that is, part B, wherein part A (a) has a silyl-modified organic polymer having two or more (R) m (Y 1 ) 3-m -Si groups [wherein each R is a hydroxyl group or a hydrolyzable group, each Y 1 is an alkyl group having 1 to 8 carbon atoms, and m is 1, 2, or 3], which is an organic polymer selected from polyethers, hydrocarbon polymers, acrylate polymers, polyesters, polyurethanes, and polyureas and (b) a reinforcing filler, and the catalyst package, that is, part B, (i) a condensation catalyst, and (ii) a crosslinking agent, (iia) having a structure R 6 j Si(OR 5 ) 4-j [wherein each R 5 may be the same or different and is an alkyl group having 2 or more carbon atoms, j is 1 or 0, R 6is a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 2 or more carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a silicon-bonded organic group selected from any one of the foregoing, wherein one or more hydrogen atoms bonded to carbon are substituted by halogen atoms, or an organic group having an epoxy group, a glycidyl group, an acyl group, a carboxyl group, an ester group, an amino group, an amide group, a (meth)acrylic group, a mercapto group, or an isocyanate group] of silane, (iib) structure R 7 Si(OMe)3 [wherein, R 7 is R 6 however, the molecular weight is 190 or more] of silane, (iic) structure (R’O)3Si(CH2) n N(H)-(CH2) z NH2 [wherein, each R’ may be the same or different and is an alkyl group having 1 to 10 carbon atoms, n is 2 to 10, and z is 2 to 10] of silane, (iid) structure (R 4 O) r (Y 2 ) 3-r -Si(CH2) x -((NHCH2CH2) t -Q(CH2) x ) w -Si(OR 4 ) r (Y 2 ) 3-r [wherein, R 4 is a C1 - 10 alkyl group, Y 2 is an alkyl group having 1 to 8 carbon atoms, Q is a chemical group containing a heteroatom having a lone pair, each x is an integer from 1 to 6, t is 0 or 1, each r is independently 1, 2, or 3, and w is 0 or 1] of a bipodal silane, or (iie) A mixture of two or more of (iia), (iib), (iic), and (iid), A crosslinking agent selected from the group consisting of, and optionally, (iii) Two or more (R) in one molecule m (Y 1 ) 3-m A silyl-modified organic polymer (a) having a -Si group, and / or (iv) A filler, a composition comprising, A two-part formulation is provided that is mixed together shortly before application.

[0082] The process may involve fitting and engaging the lens of the lamp to the front opening of the lamp chamber, and mixing the compositions of part A and part B in a predetermined ratio, for example, part A: part B is 15:1 to 1:1, for example, about 10:1. The resulting adhesive composition is then applied onto the space / junction between the front lens engaged at the front opening of the lamp chamber and the lamp chamber, causing the composition to cure, i.e., curing the composition, thereby sealing the junction between the front lens and the lamp chamber.

[0083] This process may also include applying a coating of the anti-haze coating composition onto at least one surface of the front lens, i.e., the inner surface. The coating is applied to have a thickness of 1 to 100 μm when dried / cured.

[0084] Adhesives as described above can be used in various applications, for example, outdoor lighting, decorative lighting, for example, vehicle lamps for automobiles, trucks, motorcycles, and boat lamps, and other vehicle lamps, lighting applications, and practically any other application where a condensation-curing adhesive with low volatile by-products is required, for example, to seal the housing / box of electronic components. Examples of vehicle lamps include headlamps, brake lamps, running lamps, direction indicator lamps, fog lamps, backup lamps, and parking lamps.

Examples

[0085] For all viscosities mentioned, measurements were taken at 25 °C using a Brookfield® HAF viscometer with spindle number 3 at 10 rpm.

[0086] A series of examples were prepared and compared to two parts of reference materials. The formulations of the two parts of reference materials are shown in Tables 1a and 1b below.

Table 1

[0087] The calcium carbonate used was a stearic acid-treated commercial calcium carbonate sold under the name Calofort® SM EA by Speciality Minerals Inc.

Table 2

[0088] The treated silica used in the catalyst package was AEROSIL® 974 from Evonik. The reference composition was mixed at a weight ratio of part A: part B of 13:1. A series of examples were prepared and tested according to the compositions described herein. The compositions are presented in Tables 2a and 2b below.

Table 3

[0089] VORANOL™ 3003LM is a hydroxyl-terminated polypropylene ether from The Dow Chemical Company. The antioxidants Irganox® 1135 and Irganox® 1076 are commercial antioxidants from BASF. References to with and without urethane bonds are equivalent to k being 1 (with) and 0 (without) with respect to the urethane bonds described previously and presented below. (R) m (Y 1 ) 3-m -Si-D-[NH-C(=O)] k -

Table 4

[0090] The compositions of Examples 1, 4, and 5 were mixed at a weight ratio of Part A: Part B of 10:1. The compositions of Examples 2 and 3 were mixed at a weight ratio of Part A: Part B of 3:1. In all cases, i.e., in both the reference examples and the examples, both the composition of Part A and the composition of Part B were individually prepared using a high-speed mixer at 23 °C and a relative humidity of 50% at 2000 revolutions per minute (rpm) for 40 seconds. The pre-mixed composition of Part A and the composition of Part B were then mixed together again at 2000 rpm for 40 seconds under the same conditions in a high-speed mixer at the above ratios.

[0091] The above compositions were evaluated for physical properties as shown in Table 3 below. The test was advanced to measure the effect of by-products and volatile substances from the adhesive composition in an enclosed space on the anti-haze coating. The substrate was coated with a commercially available anti-haze coating. The test protocol is described below and was used for all examples and comparative examples.

[0092] Anti-Haze Coating (AHC) Compatibility Test Method - Determination of the Compatibility of a Silicone Adhesive with Two Commercially Available Anti-Haze Coatings (AHCs) To avoid ambiguity, the compatibility regarding this test is intended to mean a determination of whether the intended water film-forming effect provided by applying a commercially available AHC on the internal closed surface of the sample piece is altered by by-products and residual cross-linking agent materials from the silicone adhesive.

[0093] The SMP adhesive to be tested was first prepared by mixing the A part and the B part using a high-speed mixer at an A part:B part ratio of 10:1. After mixing approximately 1.0 g of the resulting uncured adhesive, the product was placed on the bottom of an Alu-Cup (Alu-Kappen Art.-Nr. 3621313 (32×30 mm), manufactured by SCHUETT-BIOTEC GMBH, hereinafter referred to as "Alu-Cup"). Subsequently, the open end of the Alu-cup was covered and closed by placing a polycarbonate (PC) plate, which had been pre-coated with an anti-haze coating on top, to ensure complete closure. The PC plate was fixed in place to ensure that the silicone adhesive and the AHC shared the same atmosphere as in the case of the typical curing time of the silicone adhesive. Then, the Alu-Cup was left for 7 days to fully cure the adhesive. During the curing process, considering that it was due to a condensation curing process, it should be understood that by-products and residual cross-linking agents evaporated into the atmosphere inside the cup and might have mixed into the AHC on the inward-facing surface of the polycarbonate strip and had an impact.

[0094] After a 7-day curing period, a second Alu-Cup was filled with water and heated to 75 °C on a laboratory hot plate. Then, the PC plate was removed from the original Alu-Cup and placed on the opening of the second Alu-Cup, with the AHC coating facing the water inside. Subsequently, the interaction between the hot water and the AHC coating surface was observed to determine the effectiveness of the AHC regarding hazing / fogging. The reaction of the AHC to the hot water and its water film formation characteristics when the AHC was in contact with water vapor could be evaluated. 1. This analysis was carried out for 30 seconds. As an alternative to observation, the results could be photographed. The observation could be recorded by a camera or video. 2. Then, the samples were ranked as follows. a. Hazy surface, bottom of the alu-cup not visible → There are sufficient contaminants in the AHC. b. Clear surface, bottom of the alu-cup not visible, fine water droplets → There are contaminants in the AHC. c. Clear surface, bottom of alu-cup visible, large water droplets → There may be contaminants in the AHC. d. Clear surface, bottom of alu-cup visible, water film → There are no contaminants in the AHC. 3. The silicone adhesives ranked in (c) and (d) (acceptance criteria) can be ranked for compatibility.

[0095] A series of standard physical property tests were conducted to confirm that the adhesive has the physical properties necessary for it to function as an adhesive. The results are also shown in Table 3 together with the details of the standard test methods.

[0096] The snap time is measured by gently touching a spatula on the surface of the cured composition at regular time intervals (typically 2 - 3 minutes). As curing progresses, the coating gains viscosity and elasticity. When these two are high enough, the coating "snaps off" the spatula. The elapsed time between the first observation of the casting and snapping effect of the coating is recorded as the snap time. This value has practical importance as it provides an indicator of the working time of the coating. The working time is defined as the time during which the applicator can cooperate with the material before reaching a viscosity high enough to prevent the applicator from being properly handled and processed. The snap time is used as a rough estimate of the working time. In this case, Base 2 was mixed with the catalyst package for the measurement of the snap time.

[0097] Also, the double shear test was conducted as follows. Double shear tensile strength Specimen coupons sized 1 mm × 25 mm × 100 mm were cleaned with isopropyl alcohol and then by plasma treatment before being tested.

[0098] A sample of the composition (Part A + Part B) with a minimum bond thickness of 0.76 and sufficient to meet a 25 mm overlap was applied in a laminator onto the surface of a pre-cleaned first substrate coupon (polypropylene). Then, a second substrate (polycarbonate that had been plasma-treated previously) was placed on top of the composition applied to the first substrate to obtain a pre-sized overlap. The two substrates were compressed and excess composition removed. The sample of the composition in the pre-sized overlap sandwiched between the two substrates was cured at room temperature for 7 days and then, using an Instron® 3366 instrument, the lap shear tensile strength was determined by pulling apart the pre-sized overlap by shear, not by peel (180° tension), at a rate of 2.0 cm / min.

[0099] Cohesive failure (CF) is observed when the cured elastomer / adhesive itself breaks without separating from the substrate surface. If the failure was not due to CF, it was considered to be due to adhesive failure (AF). Adhesive failure (AF) refers to the state where the sample is cleanly separated (peeled) from the substrate surface. In some cases, a mixed failure mode was observed. That is, some regions were peeled (i.e., AF), while some remained covered with the cured elastomer / adhesive (i.e., CF). In such cases, the percentage showing CF (CF%) was recorded (keeping in mind that CF% + AF% = 100%). [Table 5]

[0100] When used in the anti-haze test, the reference material was found to have many visible water droplets on the surface of the anti-haze coating in the test and also to result in a very hazy appearance. However, in each case, in all of the examples described herein, a transparent anti-haze coating without droplets was obtained, and thus it can be interpreted that it does not adversely affect the anti-haze coating. Furthermore, the physical properties of the examples showed good results, indicating that all of the various examples tested could be lamp adhesives, which showed that post-curing did not release by-products / cross-linking agents that interacted poorly with the anti-haze coating, and thus enabled the anti-haze coating to function.

Claims

1. A two-component condensation-curing silyl-modified polymer-based adhesive composition comprising a base part, i.e., part A, and a catalyst package, i.e., part B, wherein the base part, i.e., part A, (a) an organic polymer which is a polyether and is a silyl-modified organic polymer having two or more (R) ｍ (Y １ ) ３－ｍ -Si groups [wherein each R is a methoxy group or an ethoxy group, each Y １ is an alkyl group having 1 to 8 carbon atoms, and m is 1, 2, or 3], and (b) one or more reinforcing fillers selected from precipitated calcium carbonate, precipitated silica, and fumed silica, and and wherein the catalyst package, i.e., part B, (i) a tin-based catalyst, and (ii) a crosslinking agent, which is (iic) a silane of the structure (R'O) ３ Si(CH ２ ) ｎ N(H)-(CH ２ ) ｚ NH ２ [wherein each R' may be the same or different and is an alkyl group having 1 to 10 carbon atoms, n is 2 to 10, and z is 2 to 10], and (iid) a silane of the structure (R ４ O) ｒ (Y ２ ) ３－ｒ -Si(CH ２ ) ｘ -((NHCH ２ CH ２ ) ｔ -Q(CH ２ ) ｘ ) ｗ -Si(OR ４ ) ｒ (Y ２ ) ３－ｒ [wherein, R ４ is a C1-10 alkyl group, Y ２ is an alkyl group having 1 to 8 carbon atoms, Q is a chemical group containing a heteroatom having a lone pair, each x is an integer from 1 to 6, t is 0 or 1, each r is independently 1, 2, or 3, and w is 0 or 1] of the two-legged silane A crosslinking agent, which is a mixture consisting only of and optionally, (iii) a silyl-modified organic polymer (a) having two or more (R) ｍ (Y １ ) ３－ｍ -Si groups, and / or (iv) a filler, and the two-component condensation-curing silyl-modified polymer-based adhesive composition contains no silyl-modified organic polymer other than the polymer (a) in part A and the polymer (a) in part B, polysiloxane polymer, and no crosslinking agent other than the silane (ii) in part B. A two-component condensation-curing silyl-modified polymer-based adhesive composition.

2. The two-component condensation-curing silyl-modified polymer-based adhesive composition according to claim 1, wherein the reinforcing filler (b) in part A is precipitated calcium carbonate, and the optional filler (iv) in part B is ground calcium carbonate, precipitated calcium carbonate, precipitated silica, and / or fumed silica.

3. The two-component condensation-curable silyl-modified polymer-based adhesive composition according to claim 1, wherein the catalyst (i) is a tin catalyst selected from tin triflate, triethyltin tartrate, tin octoate, tin oleate, tin naphthenate, butyltin tri-2-ethylhexoate, tin butyrate, carbomethoxyphenyltin trisbehenate, isobutyltin triceroate, dibutyltin dilaurate, dimethyltin dibutyrate, dibutyltin dimethoxide, dibutyltin diacetate, dimethyltin bisneodecanoate, dibutyltin dibenzoate, stannous octoate, dibutyltin bis(2,4-pentanedionate), dimethyltin dineodecanoate, and dibutyltin dioctoate.

4. Both the polymer (a) in part A and the polymer (a) in part B are (R) ｍ (Y １ ) ３－ｍ -Si-D-[NH-C(=O)] ｋ - [In the formula, each R is a hydroxyl group or a hydrolyzable group, each Y １ is an alkyl group having 1 to 8 carbon atoms, m is 1, 2, or 3, D is a divalent C ２－６ alkylene group, and k is 1 or 0] and is a polyether having a terminal of the two-component condensation-curable silyl-modified polymer-based adhesive composition according to claim 1.

5. The two-component condensation-curable silyl-modified polymer-based adhesive composition according to claim 1, wherein carbon black as a pigment and / or non-reinforcing filler is present in part B, that is, in the catalyst package, in an amount of 1 to 30% by weight of the catalyst package.

6. Based on the total weight% of the catalyst package being 100% by weight for part B, a condensation-curing catalyst (i) in an amount of 0.5 to 40% by weight based on the weight of the catalyst package, a crosslinking agent (ii) in an amount of 1 to 80% by weight based on the weight of the catalyst package, and optionally Based on the weight of the catalyst package, in an amount of 0 to 98.5% by weight, of two or more (R) in one molecule ｍ (Y １ ) ３－ｍ -Si group-containing silyl-modified organic polymer (iii), and / or Based on the weight of the catalyst package, in an amount of 0 to 40% by weight of a filler, The two-component condensation-curable silyl-modified polymer-based adhesive composition according to claim 1, comprising [

7. ] The two-component condensation-curable silyl-modified polymer-based adhesive composition according to claim 1, wherein part A, i.e., the base part, and part B, i.e., the catalyst package, are mixed at a weight ratio of 15:1 to 1:1.

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