CA2167185A1 - Uv-curable block copolymer composition - Google Patents
Uv-curable block copolymer compositionInfo
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- CA2167185A1 CA2167185A1 CA002167185A CA2167185A CA2167185A1 CA 2167185 A1 CA2167185 A1 CA 2167185A1 CA 002167185 A CA002167185 A CA 002167185A CA 2167185 A CA2167185 A CA 2167185A CA 2167185 A1 CA2167185 A1 CA 2167185A1
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- block copolymer
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- composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Graft Or Block Polymers (AREA)
Abstract
UV-curable block copolymer composition comprising: (a) 100 parts by weight of a block copolymer comprising at least one polymer block A derived from monovinyl aromatic compound and at least one polymer block B derived from a conjugated diene, wherein: the content of monovinyl aromatic compound is in the range of from 5 to 50 % by weight based on the total weight of block copolymer; each block A has an apparent molecular weight in the range of from 1,000 to 50,000; and each block B has an apparent molecular weight in the range of from 10,000 to 250,000; and (b) 0.5-30 parts by weight of at least one photoinitiator, characterized in that the block copolymer is a multi-armed block copolymer and at least one photoinitiator is used containing a carbonyl group which is directly bonded to at least one aromatic ring structure.
Description
2 t S 7 ~ & 5 PCT~EP94/02314 W -CURABLE BLOCK COPOLYMER COMPOSITION
The present invention relates to a W -curable block copolymer composition. More specifically, the present invention relates to a W -curable block copolymer composition for adhesives, sealants and coatings comprising an elastomeric block copolymer and at least one photoinitiator.
From PCT application No. WO 88/01281 a radiation curable rubber-based pressure-sensitive adhesive composition is known comprising at least one elastomeric rubber-based adhesive and a polythiol as the cross-linking agent. This composition can be cured by exposure to either electron beam radiation or W irradiation. In the latter case, the additional presence of a photoinitiator is required. The presence of a cross-linking agent, in particular a polythiol, is taught to be essential for obtaining a cured pressure-sensitive adhesive composition having good adhesion properties and elevated temperature shear.
~owever, it would be attractive for economical and processing reasons to reduce the number of components and still obtain a cured adhesive composition having excellent properties, also at elevated temperatures.
U.S. Patent No. 5,093,406 discloses a pressure-sensitive adhesive comprising a free radical cured product formed by e.g. W
curing of a mixture containing:
(a) 15-60 parts by weight (pbw) of an unsaturated elastomer component, suitably comprising styrene-isoprene diblock and styrene-isoprene-styrene triblock copolymers, (b) 85-40 pbw of a hydrogenated styrene based tackifying resin, (c) 0-15 pbw of a reinforcing resin for the polystyrene endblock of the elastomer component, and (d) 0-10 pbw of a polythiol cross-linking agent.
W O 95/02640 .~ t ~ ~ ~ $5~ PCT~EP94/02314 Although the presence of a polythiol cross-linking agent is left optional, it is clearly a preferred embodiment, which for instance becomes readily apparent from the working examples, where only compositions cont~ining a polythiol cross-linking agent are described.
Hence, the need for a W -curable composition, which does not require the presence of a cross-linking agent for an effective curing and which can be suitably applied in e.g. hot melt adhesive compositions, still remains.
Often, rubber-based hot melt adhesive, sealant and coating compositions which do not contain any cross-linking agent, need to be cured in an atmosphere containing as little oxygen as possible.
Upon exposure to W irradiation namely, the aliphatic double bonds present in the rubber will open thus forming free radicals. The various rubber polymer chains cont~ining free radicals along the polymer chains interact with each other through said free radicals as a result of which the desired cross-linking is accomplished.
However, the free radicals also readily react with oxygen to form peroxides. It will be appreciated that-the formation of such peroxides seriously hampers the cross-linking reaction.
Consequently, curing of rubber based compositions which do not contain any cross-linking agent is conveniently performed in an inert gas atmosphere, most suitably in a nitrogen atmosphere. It will be understood that the requirement of an oxygen-poor atmosphere seriously hampers the commercial development of UV
curing of rubber-based hot melt adhesives, sealants and coatings which are free of cross-linking agent.
It would therefore be advantageous if W curing could be performed in an atmosphere, wherein oxygen is present in minor traces up to normal amounts, i.e. from about as little as l volume % to the normal value in air of about 21 volume %. From a commercial as well as an economical point of view it is highly attractive to operate in relatively oxygen rich atmospheres, as no expensive equipment and specific precautions are necessary to ensure an oxygen-free atmosphere.
~ ~Pat~nt~r.~lir-ti~nNo.rcT~4lo2il~
~ru~k~xempla~ 2l67l85 ~
:lence, it is an objecl of the present inven~-c~ to provide a b __k copolymer composition which can be effec_:-e:y cured by exp3sure to UV radiation wi-hout using any cross-:_n.king agent.
I- addition, it is an objec~ of the present inve~ on to provide a W --urable hot melt adhesive, sealant or coatins --~position which dces not require the presence of any cross-link -- ~gent and which car. be readily cured in an oxygen-containing at~cs_nere.
Accordingly, the prescnt invention relates _~ ~ JX-curable b:-ck copolymer composition comprising:
'a) 100 parts by weight (pbw~ of a multiarme~ lock copolymer comprising at least one polyr.e- biock A
derived from a monovinyl aromatic com?c_nc and at least one polymer block 3 derived from a con -_gated diene, wherein:
- the content of monovinyl aromatic ~o.m?ound is in the range of from S to 50~ by weight -ase on the total weight of block copolymer;
- each block A has an apparent molec_lar weight in the range of from 1,000 to 50,000; anc - each block B has an apparent molec_ia_ weight in the range of from 10,000 to 250,000; ar^
(b) from 0.5 to 30 pbw, preferably from 5 =: 20 pbw, of at least one photoini.iator, characterised in that the multi-armed block ^_?olymer has the structure according to any one of the genera: _ormulae:
(AB)nX, (8A)nX, (ABA)nX, (BAB)nX or (AB ? B)qX~
wherein A is a polymer block derived from a .~onovinyl aromatic compound, wherein B is a polymer block derived from a conjugated diene, wherein n represents an i-~eger of 2 or higher and p and q represent an integer of : o- higher~and wherein X is the residue of the coupling agen~ used, that at least one photoinitiator is used, containirg a carbonyl group whlch is directly bound to at least one ar^r.at-c ring structure;
AMENDED S~ET
JO2~X~
T 'PatentAr~liri~ No.PCT~P94/02314 that said somposition is free Crom ~ c:oss-linking agent and that it is curable ln an oxygen-con=ai.ing atmosphere.
With the expression "apparent molec~ia- weight" as used throughout this description, the mo_ecuiar weight as determined by Gel Permeation Chroma=ography using polystyrene calibration standards is meant.
AMENDED S~
~ In Idl Patent~;, No. PC.T/EP94/02314 (4) Commor coupling agents are for instance divinyl be-.--ne, silic^n tetrachloride, gamma glycidoxy-propyl-trime--cxyl-silane and dibromoethane. A preferred block copol~...e- has the general formula (AB)nX with A and B as previous:y define~, n representing an integer in the range of --^m 3 to 20, pr-ferably 4 to 12, and X representing a coupl~ agent residue, preferably t~e residue of divinyl benzene. The multi--rmed block copolymers may be prepared by cou-::ng living sequentially prepared intermediate polymer ~ ns by using any conventional coupIing techniques, such as e.g. d sclosed in U.S. Patents Nos. 3,231,635i 3,43:,323;
The present invention relates to a W -curable block copolymer composition. More specifically, the present invention relates to a W -curable block copolymer composition for adhesives, sealants and coatings comprising an elastomeric block copolymer and at least one photoinitiator.
From PCT application No. WO 88/01281 a radiation curable rubber-based pressure-sensitive adhesive composition is known comprising at least one elastomeric rubber-based adhesive and a polythiol as the cross-linking agent. This composition can be cured by exposure to either electron beam radiation or W irradiation. In the latter case, the additional presence of a photoinitiator is required. The presence of a cross-linking agent, in particular a polythiol, is taught to be essential for obtaining a cured pressure-sensitive adhesive composition having good adhesion properties and elevated temperature shear.
~owever, it would be attractive for economical and processing reasons to reduce the number of components and still obtain a cured adhesive composition having excellent properties, also at elevated temperatures.
U.S. Patent No. 5,093,406 discloses a pressure-sensitive adhesive comprising a free radical cured product formed by e.g. W
curing of a mixture containing:
(a) 15-60 parts by weight (pbw) of an unsaturated elastomer component, suitably comprising styrene-isoprene diblock and styrene-isoprene-styrene triblock copolymers, (b) 85-40 pbw of a hydrogenated styrene based tackifying resin, (c) 0-15 pbw of a reinforcing resin for the polystyrene endblock of the elastomer component, and (d) 0-10 pbw of a polythiol cross-linking agent.
W O 95/02640 .~ t ~ ~ ~ $5~ PCT~EP94/02314 Although the presence of a polythiol cross-linking agent is left optional, it is clearly a preferred embodiment, which for instance becomes readily apparent from the working examples, where only compositions cont~ining a polythiol cross-linking agent are described.
Hence, the need for a W -curable composition, which does not require the presence of a cross-linking agent for an effective curing and which can be suitably applied in e.g. hot melt adhesive compositions, still remains.
Often, rubber-based hot melt adhesive, sealant and coating compositions which do not contain any cross-linking agent, need to be cured in an atmosphere containing as little oxygen as possible.
Upon exposure to W irradiation namely, the aliphatic double bonds present in the rubber will open thus forming free radicals. The various rubber polymer chains cont~ining free radicals along the polymer chains interact with each other through said free radicals as a result of which the desired cross-linking is accomplished.
However, the free radicals also readily react with oxygen to form peroxides. It will be appreciated that-the formation of such peroxides seriously hampers the cross-linking reaction.
Consequently, curing of rubber based compositions which do not contain any cross-linking agent is conveniently performed in an inert gas atmosphere, most suitably in a nitrogen atmosphere. It will be understood that the requirement of an oxygen-poor atmosphere seriously hampers the commercial development of UV
curing of rubber-based hot melt adhesives, sealants and coatings which are free of cross-linking agent.
It would therefore be advantageous if W curing could be performed in an atmosphere, wherein oxygen is present in minor traces up to normal amounts, i.e. from about as little as l volume % to the normal value in air of about 21 volume %. From a commercial as well as an economical point of view it is highly attractive to operate in relatively oxygen rich atmospheres, as no expensive equipment and specific precautions are necessary to ensure an oxygen-free atmosphere.
~ ~Pat~nt~r.~lir-ti~nNo.rcT~4lo2il~
~ru~k~xempla~ 2l67l85 ~
:lence, it is an objecl of the present inven~-c~ to provide a b __k copolymer composition which can be effec_:-e:y cured by exp3sure to UV radiation wi-hout using any cross-:_n.king agent.
I- addition, it is an objec~ of the present inve~ on to provide a W --urable hot melt adhesive, sealant or coatins --~position which dces not require the presence of any cross-link -- ~gent and which car. be readily cured in an oxygen-containing at~cs_nere.
Accordingly, the prescnt invention relates _~ ~ JX-curable b:-ck copolymer composition comprising:
'a) 100 parts by weight (pbw~ of a multiarme~ lock copolymer comprising at least one polyr.e- biock A
derived from a monovinyl aromatic com?c_nc and at least one polymer block 3 derived from a con -_gated diene, wherein:
- the content of monovinyl aromatic ~o.m?ound is in the range of from S to 50~ by weight -ase on the total weight of block copolymer;
- each block A has an apparent molec_lar weight in the range of from 1,000 to 50,000; anc - each block B has an apparent molec_ia_ weight in the range of from 10,000 to 250,000; ar^
(b) from 0.5 to 30 pbw, preferably from 5 =: 20 pbw, of at least one photoini.iator, characterised in that the multi-armed block ^_?olymer has the structure according to any one of the genera: _ormulae:
(AB)nX, (8A)nX, (ABA)nX, (BAB)nX or (AB ? B)qX~
wherein A is a polymer block derived from a .~onovinyl aromatic compound, wherein B is a polymer block derived from a conjugated diene, wherein n represents an i-~eger of 2 or higher and p and q represent an integer of : o- higher~and wherein X is the residue of the coupling agen~ used, that at least one photoinitiator is used, containirg a carbonyl group whlch is directly bound to at least one ar^r.at-c ring structure;
AMENDED S~ET
JO2~X~
T 'PatentAr~liri~ No.PCT~P94/02314 that said somposition is free Crom ~ c:oss-linking agent and that it is curable ln an oxygen-con=ai.ing atmosphere.
With the expression "apparent molec~ia- weight" as used throughout this description, the mo_ecuiar weight as determined by Gel Permeation Chroma=ography using polystyrene calibration standards is meant.
AMENDED S~
~ In Idl Patent~;, No. PC.T/EP94/02314 (4) Commor coupling agents are for instance divinyl be-.--ne, silic^n tetrachloride, gamma glycidoxy-propyl-trime--cxyl-silane and dibromoethane. A preferred block copol~...e- has the general formula (AB)nX with A and B as previous:y define~, n representing an integer in the range of --^m 3 to 20, pr-ferably 4 to 12, and X representing a coupl~ agent residue, preferably t~e residue of divinyl benzene. The multi--rmed block copolymers may be prepared by cou-::ng living sequentially prepared intermediate polymer ~ ns by using any conventional coupIing techniques, such as e.g. d sclosed in U.S. Patents Nos. 3,231,635i 3,43:,323;
3,251,'05; 3,390,207; 3,598,887 and 4,219,627.
The monovinyl aromatic compound may be selected frcm styrene, a-methylstyrene, o-methylstyrene, p-methy_s-yrene, p-tert-Dutyl-styrene, 1,3-dimethylstyrene or mixtur_s thereo , of which styrene is most preferred.
Suitab:e conjugated dienes to be used in the block _~polymer of com?onent (a) are 1,3-butadiene, 2-methyl-1,3-bu~_d-ene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadie-.e, 1,3-he~adiene or mixtures thereof, of which 1,3-buta^ ene, isopre~.e or mixtures thereof are the preferred monc..e-s.
Isoprene is most preferred.
; As already indicated supra, it is preferred that th_ ^:ock copolymer is a multi-armed styrene(S)-isoprene(I) c-styrene-butadiene(B~ block copolymer having a styren-conten~ in the range of from S to 25~ by weight. Ar. -~ample of a c_mmercially available multi-armed S-I block c_-o ymer is KRA~ON D-1320X (KRATON is a trade mark).
VDS2033 ~ENOED SHEET
-~O 95/02640 ~ 1 ~ 7 1 ~ 5 PCT~EP94/02314 The photoinitiator component (b) in the block copolymer composition according to the present invention may be composed of one or a combination of two or more photoinitiators. In any event, at least one of the photoinitiators used must be a compound cont~ining a carbonyl group which is directly bonded to at least one aromatic ring structure. It is preferred that this photoinitiator is selected from the group consisting of:
(l) at least one benzophenone of the general formula (I) R2 ~ R3 ~ R6 (I) wherein Rl to R8 independently represent hydrogen or an alkyl group having from l to 4 carbon atoms, preferably methyl, and wherein R7 and/or R8 represent in addition alkoxy of l to 4 carbon atoms and wherein n has a value of 0, l or 2, optionally in combination with at least one tertiary amine, (2) at least one sulphur-containing carbonyl compound, wherein the carbonyl group is directly bound to at least one aromatic ring, preferably of the general formula II
R1 ~R1 ~
wherein R , R , R each may represent hydrogen, alkyl of 1-4 carbon atoms or an alkylthio group, having l to 4 carbon atoms, and (3) mixtures of (l) and (2).
W O 95/02640 2 ~ ~ 7 T ~ 5 PCT~EP94/02314 Examples of suitable compounds of category (1) are benzo-phenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone and an eutectic mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzo-phenone (ESACURE TZT) and 2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE 651) (ESACURE and IRGACURE are trade marks). These compounds may be employed in combination with tertiary amines, such as e.g. W ECRYL 7100 ( W ECRYL is a trade mark).
Category (2) embraces compounds such as e.g. 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, commercially available as IRGACURE 907 (IRGACURE is a trade mark).
An example of suitable mixtures (category (3)) is a mixture of 15% by weight of a mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone, and 85% by weight of a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone. This mixture is commercially available under the trade name ESACURE X15.
Photoinitiators of any one of the above categories (1), (2) and (3) may also be used in combination with other photoinitiators, such as e.g. W ECRYL P115. Particularly useful is a combination of benzophenone and said W ECRYL P115.
In a preferred embodiment of the present invention the photoinitiator is selected from the group consisting of (i) benzophenone, (ii) a mixture of benzophenone and a tertiary amine containing a carbonyl group which is directly bonded to at least one aromatic ring, and (iii) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-l. Of these 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1 is most preferred.
The photoinitiator should be present in an amount of from 0.5 to 30 parts by weight per 100 parts by weight of block copolymer (phr) to ensure sufficient cross-linking upon exposure to W
irradiation. It is preferred that the photoinitiator is present in an amount of from 5 to 20 phr.
The W irradiation used for cross-linking the block copolymer composition of the present invention in principle may be any W
source having an output spectra showing one or more peaks at wavelengths between 200 and 500 nanometer (nm). Particularly ~ WO 95/02640 PCT~EP94/02314 suitable W sources are Fusion bulb lamps (Fusion is a trade mark) having output maxima at 260-270 nm, 320 nm and 360 nm ("H" bulb), at 350-390 nm ("D" bulb) or at 400-430 nm ("V" bulb). Combinations of these Fusion bulb lamps may also be used. H and D bulb lamps (linear power 300 W/inch) are particularly useful, while a combination of D bulb and H bulb can also be suitably applied.
The exposure to W irradiation may be performed by any known method. A suitable method for instance is exposing a sample either in a layer obtained from a hot melt or in a layer obtained by solvent coating to W irradiation by passing said sample at a certain speed (expressed in meters per minute, m/min) underneath the W source. If necessary, the exposure to irradiation may be repeated one or more times, e.g. by repeatedly passing the sample underneath the W source or by passing the sample underneath two or more lamps positioned in series, in order to accomplish sufficient curing. The lower the total irradiation dose and the higher the speed with which the sample can be passed underneath the W source for obtaining sufficient and satisfactory curing, the better the curing ability of the said sample.
The W curable block copolymer composition according to the present invention can be suitably applied in hot melt as well as solvent adhesive compositions, sealants and coatings. When used in adhesive compositions, common additives, such as a tackifying resin, a softening oil and an antioxidant may also be present. For instance, a suitable hot melt adhesive composition may comprise in addition to the block copolymer composition of the present invention:
(c) 10-300 parts by weight per lO0 parts by weight of block copolymer (phr) of at least one resin which is compatible with the poly(conjugated diene) polymer block(s);
(d) 0-150 phr of a plasticizer; and (e) 0.5-5 phr of an antioxidant.
Suitable poly(conjugated diene) compatible resins are tackifying resins and liquid resins, such as e.g. polyterpene resins, polyindene resins, rosin esters, hydrogenated rosins, wo gs/02640 2 1 6 7 1 a 5~ PCT~EP94/02314 alpha-pinene resins, beta-pinene resins, hydrocarbon resins of petroleum origin and phenolic resins. Examples are REGALITE R91, R101, R 125 and S260 (REGALITE is a trade mark), ESCOREZ 1310 and 5380 (ESCOREZ is a trade mark), WINGTACK 95 (UINGTACK is a trade mark), FORAL 85 and 105 (FORAL is a trade mark), PICCOLYTE A115, S115 and S10 (PICCOLYTE is a trade mark) and PICCOTAC 95E. The use of resins having a low degree of unsaturation, such as REGALITE
R91, R101 or R 125, is preferred.
As a plasticizer mineral oils, both naphthenic and paraffinic oils, or low molecular weight polybutylene polymers may be used.
Examples of suitable plasticizers are SHELLFLEX 371 and 451 and TUFFLO 6204 (naphthenic oils), TUFFLO 6056 (paraffinic oil) and the polybutylenes HYVIS 200, NAPVIS 30 and NAPVIS D-10. SHELLFLEX, TUFFLO, HYVIS and NAPVIS are trade marks. Also very useful are REGALREZ 1018 (REGALREZ is a trademark), ONDINA 68 (ONDINA is a trade mark) and V-OIL 7047 (V-OIL is a trade mark).
As component (e) any antioxidant commonly applied in adhesive formulations may be used. An example of such antioxidant is the phenolic compound IRGANOX 1010 (IRGANOX is a trade mark).
In addition to the components (c), (d) and (e) other additives, such as endblock compatible resins, W stabilizers, fillers, flame retarders and the like, may be present as well depending on the specific conditions under which the hot melt adhesive composition is to be used.
Hot melt adhesive compositions, sealant compositions and coating compositions comprising the W -curable block copolymer composition described hereinbefore also form part of the present invention. The same applies for cured compositions obtained by exposing said adhesive, sealant and coating compositions to W
irradiation-The invention is further illustrated by the following examples, however without restricting the scope of the invention to these specific embodiments.
The photoinitiators used in the examples have been abbreviated as follows:
-~0 95/02640 2 1 6 ~ 1 8 5 PCTAEP94/02314 TZT : ESACURE TZT I184 : IRGACURE 184 X15 : ESACURE X15 I651 : IRGACURE 651 P115 : W ECRYL P115 I907 : IRGACURE 907 W EC : W ECRYL 7100 Benz : Benzophenone Unless otherwise mentioned, the samples were irradiated by a W source while being exposed to a soft flow of nitrogen. This flow of nitrogen was such that oxygen was still present during irradiation. Accordingly, irradiation took place in the presence of up to 10 volume % of oxygen.
Example 1 A formulation consisting of a multi-armed S-I block copolymer, two polyisoprene compatible resins and an antioxidant was prepared by intimately mixing:
100 pbw of KRATON D-1320X, 150 phr REGALITE R91, 60 phr REGALREZ 1018, and 1 phr IRGANOX 1010.
KRATON D-1320X is a multi-armed block copolymer consisting of S-I
block copolymer arms. The coupling agent used is divinylbenzene. It has a polystyrene content of 10% by weight. The apparent molecular weight of each S-I arm is about 100,000 and the peak molecular weight of each polystyrene block is about 11,000. The total number of arms may vary from 6 to 100 and usually is between 6 and 40.
To this formulation several photoinitiators were added after which the compositions thus obtained were exposed to W irradiation by passing the formulation as a hot melt underneath a single Fusion D bulb lamp (F300; 300 W/inch) at a speed of 5 m/min. Of these compositions the Shear Adhesion Failure Temperature (SAFT) was measured. A value of 140 C or higher is acceptable. The results are listed in Table I.
W O 95/02640 2 1 6 ~ t ~ 5~ PCT~EPg4/02314 _ TABLE I W curing of several formulations photoinitiator (pbw) TZT X15 I651 I184 W EC SAFT (C) 1 pass 2 passes 110 >160 >160 >160 114 >160 >160 >160 3 2 10 >160 >160 151 >160 >160 >160 >160 >160 From table I it is clear that all formulations show excellent SAFT
values after 2 passes underneath the D bulb W lamp, (300 W/inch) while five formulations already give excellent SAFT values, i.e.
>160 C, after only 1 pass.
Examp;e 2 The same base formulation as used in Example 1 was employed for the evaluation of the effect on the SAFT values of the speed with which a formulation is passed underneath various W sources.
The photoinitiator used was IRGACURE 907 in an amount of 5 pbw per 100 pbw of block copolymer. When two bulb lamps were positioned in series (indicated as D+V, D+H and D+D), the exposure to the irradiation originating from the second lamp took place in air, so without applying a nitrogen flow. The results are listed in table II; the SAFT values listed are given in C.
~qo gs/02640 2 1 6 7 1 8 5 PCT~EP94/02314 TABLE II SAFT values after W curing at different speeds and with different W lamps Speed D bulb D+H bulb D+V bulb D+D bulb (m/min) l pass 2 passes 1 pass 1 pass 1 pass >160 >160 >160 >160 >160 112 >160 >160 >160 123 104 131 >160 118 105 The H and V bulb had a linear power of 300 W/inch (120 W/cm) From table II it is clear that particularly the combination of a D
bulb lamp followed by a H bulb lamp gives excellent results, even at such high speed as 20 m/min.
Characteristic adhesive properties (loop tack and peel adhesion) were also measured of same irradiated samples as listed in Tables III and IV.
TABLE III
Looptack: Influence of the lamp and speed (N/25mm) Speed D-Bulb (l lamp) D+H Bulb D+D Bulb M./Min. 1 pass 2 passes 1 pass l pass with without with without with with without *
26 24 24* 26 22 'with': means with low N2 flow - 'without': means that the samples were cured in open atmosphere (no N2 flow).
*: zippery tack W O 95/02640 2 1 6 7 1 ~ 5 PCT~EP94/02314 TABLE IV
Peel adhesion: Influence of the lamp and speed (N/25mm) Speed D-Bulb (1 lamp) D+H Bulb D+D Bulb M./Min. 1 pass 2 passes 1 pass 1 pass with without with withoutwith with without From these tables it will be appreciated that the adhesive properties are not damaged by the curing.
Example 3 The same formulation as used in Example 2 was employed and exposed to irradiation using a Fusion H bulb lamp (F300) with and without a nitrogen flow. The formulation was exposed to irradiation by passing it at different speeds once and twice underneath the H
bulb as well as by passing it once underneath two H bulb lamps positioned in series. The SAFT values (in C) were measured after each pass. The results are listed in table V.
~0 95/02640 PCT~EP94/02314 TABLE V SAFT values after W curing with and without nitrogen flow Speed 1 lamp 2 lamps (m/min) l pass 2 passes 1 pass withwithout withwithout without 88 85 107 lO1 117 From table V it can be derived that irradiation in air, so without applying a nitrogen flow, results in excellent SAFT values which are similar to, and in some cases even better than, the SAFT values obtained by applying a nitrogen flow during exposure to irradiation.
Example 4 Several photoinitiators and combinations of photoinitiators were added to the base formulation as used in Example 1. The compositions thus obtained (compositions A to G) were cured by passing them three times (lp, 2p, 3p) at a speed of 5 m/min underneath a Fusion D bulb lamp. The SAFT values, of some compositions the Holding Power at 95 C (HP 95C) and the peel adhesion 180 were determined after each pass. The results are listed in table VI.
W O 95/02640 2 ~ 5,!1 PCT~EP94/02314 _ TABLE VI
W curing of block copolymer compositions Composition A B C D E F G
Benz 5 5 10 10 5 10 lp 150 148 157133 155~160 141 SAFT (C) 2p >160 >160 158>160 >160>160 147 3p >160 >160 159>160 >160>160 151 lp >100 >100 >100>100 >100 HP 95C 2p>100 >100 >100>100 >100 3p>100 >100 >100>100 >100 Peel- lp 20 18 16 19 16 16 10 adh. 180 2p 18 20 21 21 16 15 12 (N/25mm) 3p 21 20 18 22 17 16 13 From table VI it 'can be seen that in particular the W cured adhesive compositions A to F exhibit excellent adhesive properties.
Example 5 A formulation, comprising: KRATON D-1320 X 100 phr REGALITE R 91 150 phr RF.GATRF.7. 1018 60 phr IRGACURE 907 5 phr IRGANOX 1010 1 phr was tested with irradiation from another W -lamp, the H-bulb, which substantially emits the conventional mercury spectrum.
The SAFT test results obtained have been listed in Table VII:
- ~0 95/02640 2 1 6 7 1 8 5 PCT~EP94/02314 Table VII
~ SAFT: Influence of the H-bulb lamp (C) - Speed 1 Lamp 2 Lamps M./Min. 1 pass 2 passes 1 pass with without with without without >160 >160 99 107 137 152 >160 From this table VII it will be appreciated that the N2 is not necessary and has hardly any influence on the curing efficiency of this formulation. Moreover it appeared possible to have a good curing efficiency with two passes under the H-lamp up to 15 m/min (SAFT higher than 150 CC).
The adhesive properties of these samples have also been measured and listed in Tables VIII and IX.
wo 95/02640 2 1- ~ 7 ~ ~5 PCT~EW4/02314 Table VIII
LOOPTACK: Influence of the H-bulb lamp (N/25mm) Speed 1 Lamp 2 Lamps M./Min. 1 pass 2 passes 1 pass with without with without without * - zippery tack TABLE IX
Peel adhesion: Influence of the H-bulb lamp (N/25mm) Speed 1 Lamp 2 Lamps M./Min. 1 pass 2 passes 1 pass with without with without without From the previous results it will be appreciated that the adhesive properties are not damaged by the curing whatever the curing speed or dose.
Example 6 A similar formulation (KRATON D-1320X/REGALITE
R91/REGALREZ 1018/IRGANOX 1010;100/150/60/1) was used with a - ~O 95/02640 2 1 6 7 1 8 ~ PCT~EP94/02314 combination of benzophenon and EBECRYL 7100 (or W ECRYL 7100: both trade names exist for the same product) as photoinitiator. The - samples were irradiated under a H-bulb at different speeds. The temperature resistance results (SAFT and Holding Power 95 C) have been listed in Tables X and XI:
TABLE X
SAFT: Influence of curing speed (C) Adjusted components benz. EBECRYL 5 m./min. 10 m./min. 15 m./min. 20 m./min.
1 p 2 p 1 p 2 p 1 p 2 p1 p 2 p * = zippery tack TABLE XI
HP 95 C: Influence of curing speed (h) Adjusted components benz. EBECRYL5 m./min10 m./min15 m./min 20 m./min 500 g 1 kg500 g 1 kg500 g 1 kg500 g 1 kg 10 10 1 p > 100 6 0.07 ~ 2 p > 100 61 > 100 77 15 W O 95/02640 2 1 6 7 1 85 PCT~EP94/02314 From these data it will be clear that also good curing efficiency was obtained in open air with a combination of benzophenon and tertiary amine as photoiniator.
Example 7 1. Two radiation curable block copolymer mixtures (A and B) of molecular structure (SB) B X, wherein m + n - 4, and each of m and n had an average value of about 2, wherein X represented the residue of tetrachlorosilane, were tested in an "open air"
irradiation process with two photoinitiators covered by the present application, i.e. IRGACURE 651 and IRGACURE 907 respectively.
Further details of these polymers have been listed in Table XII.
TABLE XII
Polymer A B
% PS 12.7 10.8 % vinyl 54 56 MFR 8.1 1.4 Adhesive Composition (3) (4) (5) (6) polymer 100 phr 100 ~F.~AT.F.7. 1018 63 81 2i6718~
~ ~0 95/02640 PCTAEW4/02314 The samples were cured at different speeds, under a F-300 D-bulb lamp. These adhesive formulations were irradiated in direct - cure, with low N2 flow. The results have been listed in Table XIII.
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21671~5 -~0 95/02640 PCT~EP94/02314 2. The experimental polymers A and B of the formula (SB) B X were then cured with a more powerful lamp at higher speeds, without any nitrogen flow.
The photoinitiators IRGACURE 651 and 907 were both tested in compositions, containing the same other ingredients as specified in Table XII, i.e. formulation 4 is based on A ~olymer with IRGACURE 651, formulation 5 is based on B polymer with IRGACURE
651, formulation 6 is based on B with IRGACURE 907.
All the samples were irradiated in direct curing by means of Fusion F-600 lamps.
The results have been listed in Tables XIV and XV.
TABLE XIV
Speed D-bulb I H-bulb m./min 4 5 6 1 4 5 6 I
>170 >170 >170 1>170 >170 >170 77 >170 >170 1170 >170 >170 153 >170 1166 >170 >170 105 >170 195 >170 >170 74 86 141 186 118 >170 76 8~ 95 177 92 127 I
SAFT results (C) for samples cured under one F-600 lamp W O 95/02640 2 1 ~ 7 1 ~5 PCT~EP94/02314 TABLE XV
Speed D + D bulb I D + H bulb m./min 4 5 14 5 6 >170 >170 1>170 >170 >170 >170 >170 1150 >170 >170 111 >170 1106 147 >170 82 114 186 >170 >170 110 184 >170 >170 SAFT results (C) for samples cured under a combination of F-600 lamps It will be appreciated that improved results were obtained, when using the IRGACURE 907 photoinitiators. The best results were obtained for a B polymer based formulation irradiated by a combination of D and H bulbs. In this case, SAFT results higher than 170 C could be obtained at a speed of 60 m./min! This is the highest speed which ever could be reached in radiation curing.
Holding Power (HP) at 95 C:l kg.
Only the samples which had good temperature resistance properties were selected to perform a HP 95 C test, as listed in Table XVI.
21671~5 -~VO 95/02640 PCT~EW4/02314 TABLE XVI
Speed D-bulb I H-bulb m./min 4 (h) 5 (h) 6 (h) I 4 (h) 5 (h) 6 (h) I
10 >100 >100 >100 1 >100>100 >100 >lO0 >lO0 1 0.5/12.5 >lO0 >lO0 >lO0 1 0/429.5/>lO0 >lO0 - - >lO0 1 0 >lO0 >lO0 - - - I - - 8.6 HP 95 C results of samples cured under one F-600 lamp TABLE XVII
Speed D + D bulbs I D + H bulbs m./min4 (h)5 (h) I 4 (h) 5 (h) 6 (h) I
>lO0 >lO0 1>lO0 >lO0 >lO0 >lO0 >lO0 1l9/>lO0 >lO0 >lO0 - >lO0 1 - >lO0 >lO0 - - I - >100 >100 - - I - >lO0 >lO0 HP 95 C results of samples cured under a combination of F-600 lamps Here again we can see the good temperature performance (HP95 C > lO0 h) of the experimental polymers when using IRGACURE 907 photoinitiator. IRGACURE 907 enabled the achievement of higher curing speeds.
W O 95/02640 2 1 6 7 1 8 5 PCT~EP94/02314 From the preceding examples it will be appreciated that it became possible to effectively cure in presence of oxygen without the need of a N2 flow. High curing efficiency and temperature resistance properties achievable at high speed could be reached.
Example 8 (i) Five standard radiation sensitive compositions were prepared, comprising 100 parts by weight of each of the block copolymers contA i n i ng po ly ( s tyrene) and poly(butadiene) blocks, listed in Table XVIII, 1 part by weight of the antioxidant IRGANOX lOlO and 2 parts by weight of photosensitizer IRGACURE 651.
The last block copolymer listed in the table is not according to the claimed invention and has been included as comparative example.
TABLE XVIII Polymer characteristics Block Mol.wt. Mol.wt. Total mol.wt. Molecular Poly- Vinyl-Copolymer (xlOO0) (x1000) (x1000) form styrene (1,2-add) of S of S-B content content block block A 10.7 71 276 (SB)2B2 12.7 54 B 11.2 87 339 (SB)2B2 10.8 56 C 10.7 81 222 (SB)2B2 12.5 60.5 KRATON D 13 330 (SB)3 5 21 +/- 5 Comp. 12 45 91 SBS 40 +/- 5 From the five photosensitive compositions films of 22 micron thickness were prepared from a solvent based formulation (40% in toluene) by casting.
-~O 95/02640 2 1 ~ 7 1 8 ~ PCT~EP94/02314 The films were irradiated under a Fusion D bulb lamp in 1 pass and 2 passes respectively with a speed of 5 m/min, and the gel content was analyzed.
The gel contents have been listed in Table XIX.
TABLE XIX Gel percentage after irradiation Polymer 1 pass 2 passes A 59.5 85.5 B 81.0 86.9 C 73.8 87.5 KRATON D 1116 31.7 70.4 Comp. 0.3 9.6 (ii) Photosensitive compositions were prepared from the block copolymer identified hereinbefore as A (lOO parts by weight), IRGANOX lO10 (1 part by weight) and varying amounts of photosensitizer IRGACURE 651, as listed in the Table XX.
Films of 22 micron thickness were prepared from these compositions and the films were irradiated as described under Example 8(i). The percentage.gel after irradiation was determined.
TABLE XX % gel after irradiation Composition block Copol./AO/PS 1 pass 2 passes 100/1/1 46.2 73.3 100/1/2 59.5 85.5 100/1/4 84.7 93.7
The monovinyl aromatic compound may be selected frcm styrene, a-methylstyrene, o-methylstyrene, p-methy_s-yrene, p-tert-Dutyl-styrene, 1,3-dimethylstyrene or mixtur_s thereo , of which styrene is most preferred.
Suitab:e conjugated dienes to be used in the block _~polymer of com?onent (a) are 1,3-butadiene, 2-methyl-1,3-bu~_d-ene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadie-.e, 1,3-he~adiene or mixtures thereof, of which 1,3-buta^ ene, isopre~.e or mixtures thereof are the preferred monc..e-s.
Isoprene is most preferred.
; As already indicated supra, it is preferred that th_ ^:ock copolymer is a multi-armed styrene(S)-isoprene(I) c-styrene-butadiene(B~ block copolymer having a styren-conten~ in the range of from S to 25~ by weight. Ar. -~ample of a c_mmercially available multi-armed S-I block c_-o ymer is KRA~ON D-1320X (KRATON is a trade mark).
VDS2033 ~ENOED SHEET
-~O 95/02640 ~ 1 ~ 7 1 ~ 5 PCT~EP94/02314 The photoinitiator component (b) in the block copolymer composition according to the present invention may be composed of one or a combination of two or more photoinitiators. In any event, at least one of the photoinitiators used must be a compound cont~ining a carbonyl group which is directly bonded to at least one aromatic ring structure. It is preferred that this photoinitiator is selected from the group consisting of:
(l) at least one benzophenone of the general formula (I) R2 ~ R3 ~ R6 (I) wherein Rl to R8 independently represent hydrogen or an alkyl group having from l to 4 carbon atoms, preferably methyl, and wherein R7 and/or R8 represent in addition alkoxy of l to 4 carbon atoms and wherein n has a value of 0, l or 2, optionally in combination with at least one tertiary amine, (2) at least one sulphur-containing carbonyl compound, wherein the carbonyl group is directly bound to at least one aromatic ring, preferably of the general formula II
R1 ~R1 ~
wherein R , R , R each may represent hydrogen, alkyl of 1-4 carbon atoms or an alkylthio group, having l to 4 carbon atoms, and (3) mixtures of (l) and (2).
W O 95/02640 2 ~ ~ 7 T ~ 5 PCT~EP94/02314 Examples of suitable compounds of category (1) are benzo-phenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone and an eutectic mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzo-phenone (ESACURE TZT) and 2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE 651) (ESACURE and IRGACURE are trade marks). These compounds may be employed in combination with tertiary amines, such as e.g. W ECRYL 7100 ( W ECRYL is a trade mark).
Category (2) embraces compounds such as e.g. 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, commercially available as IRGACURE 907 (IRGACURE is a trade mark).
An example of suitable mixtures (category (3)) is a mixture of 15% by weight of a mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone, and 85% by weight of a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone. This mixture is commercially available under the trade name ESACURE X15.
Photoinitiators of any one of the above categories (1), (2) and (3) may also be used in combination with other photoinitiators, such as e.g. W ECRYL P115. Particularly useful is a combination of benzophenone and said W ECRYL P115.
In a preferred embodiment of the present invention the photoinitiator is selected from the group consisting of (i) benzophenone, (ii) a mixture of benzophenone and a tertiary amine containing a carbonyl group which is directly bonded to at least one aromatic ring, and (iii) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-l. Of these 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1 is most preferred.
The photoinitiator should be present in an amount of from 0.5 to 30 parts by weight per 100 parts by weight of block copolymer (phr) to ensure sufficient cross-linking upon exposure to W
irradiation. It is preferred that the photoinitiator is present in an amount of from 5 to 20 phr.
The W irradiation used for cross-linking the block copolymer composition of the present invention in principle may be any W
source having an output spectra showing one or more peaks at wavelengths between 200 and 500 nanometer (nm). Particularly ~ WO 95/02640 PCT~EP94/02314 suitable W sources are Fusion bulb lamps (Fusion is a trade mark) having output maxima at 260-270 nm, 320 nm and 360 nm ("H" bulb), at 350-390 nm ("D" bulb) or at 400-430 nm ("V" bulb). Combinations of these Fusion bulb lamps may also be used. H and D bulb lamps (linear power 300 W/inch) are particularly useful, while a combination of D bulb and H bulb can also be suitably applied.
The exposure to W irradiation may be performed by any known method. A suitable method for instance is exposing a sample either in a layer obtained from a hot melt or in a layer obtained by solvent coating to W irradiation by passing said sample at a certain speed (expressed in meters per minute, m/min) underneath the W source. If necessary, the exposure to irradiation may be repeated one or more times, e.g. by repeatedly passing the sample underneath the W source or by passing the sample underneath two or more lamps positioned in series, in order to accomplish sufficient curing. The lower the total irradiation dose and the higher the speed with which the sample can be passed underneath the W source for obtaining sufficient and satisfactory curing, the better the curing ability of the said sample.
The W curable block copolymer composition according to the present invention can be suitably applied in hot melt as well as solvent adhesive compositions, sealants and coatings. When used in adhesive compositions, common additives, such as a tackifying resin, a softening oil and an antioxidant may also be present. For instance, a suitable hot melt adhesive composition may comprise in addition to the block copolymer composition of the present invention:
(c) 10-300 parts by weight per lO0 parts by weight of block copolymer (phr) of at least one resin which is compatible with the poly(conjugated diene) polymer block(s);
(d) 0-150 phr of a plasticizer; and (e) 0.5-5 phr of an antioxidant.
Suitable poly(conjugated diene) compatible resins are tackifying resins and liquid resins, such as e.g. polyterpene resins, polyindene resins, rosin esters, hydrogenated rosins, wo gs/02640 2 1 6 7 1 a 5~ PCT~EP94/02314 alpha-pinene resins, beta-pinene resins, hydrocarbon resins of petroleum origin and phenolic resins. Examples are REGALITE R91, R101, R 125 and S260 (REGALITE is a trade mark), ESCOREZ 1310 and 5380 (ESCOREZ is a trade mark), WINGTACK 95 (UINGTACK is a trade mark), FORAL 85 and 105 (FORAL is a trade mark), PICCOLYTE A115, S115 and S10 (PICCOLYTE is a trade mark) and PICCOTAC 95E. The use of resins having a low degree of unsaturation, such as REGALITE
R91, R101 or R 125, is preferred.
As a plasticizer mineral oils, both naphthenic and paraffinic oils, or low molecular weight polybutylene polymers may be used.
Examples of suitable plasticizers are SHELLFLEX 371 and 451 and TUFFLO 6204 (naphthenic oils), TUFFLO 6056 (paraffinic oil) and the polybutylenes HYVIS 200, NAPVIS 30 and NAPVIS D-10. SHELLFLEX, TUFFLO, HYVIS and NAPVIS are trade marks. Also very useful are REGALREZ 1018 (REGALREZ is a trademark), ONDINA 68 (ONDINA is a trade mark) and V-OIL 7047 (V-OIL is a trade mark).
As component (e) any antioxidant commonly applied in adhesive formulations may be used. An example of such antioxidant is the phenolic compound IRGANOX 1010 (IRGANOX is a trade mark).
In addition to the components (c), (d) and (e) other additives, such as endblock compatible resins, W stabilizers, fillers, flame retarders and the like, may be present as well depending on the specific conditions under which the hot melt adhesive composition is to be used.
Hot melt adhesive compositions, sealant compositions and coating compositions comprising the W -curable block copolymer composition described hereinbefore also form part of the present invention. The same applies for cured compositions obtained by exposing said adhesive, sealant and coating compositions to W
irradiation-The invention is further illustrated by the following examples, however without restricting the scope of the invention to these specific embodiments.
The photoinitiators used in the examples have been abbreviated as follows:
-~0 95/02640 2 1 6 ~ 1 8 5 PCTAEP94/02314 TZT : ESACURE TZT I184 : IRGACURE 184 X15 : ESACURE X15 I651 : IRGACURE 651 P115 : W ECRYL P115 I907 : IRGACURE 907 W EC : W ECRYL 7100 Benz : Benzophenone Unless otherwise mentioned, the samples were irradiated by a W source while being exposed to a soft flow of nitrogen. This flow of nitrogen was such that oxygen was still present during irradiation. Accordingly, irradiation took place in the presence of up to 10 volume % of oxygen.
Example 1 A formulation consisting of a multi-armed S-I block copolymer, two polyisoprene compatible resins and an antioxidant was prepared by intimately mixing:
100 pbw of KRATON D-1320X, 150 phr REGALITE R91, 60 phr REGALREZ 1018, and 1 phr IRGANOX 1010.
KRATON D-1320X is a multi-armed block copolymer consisting of S-I
block copolymer arms. The coupling agent used is divinylbenzene. It has a polystyrene content of 10% by weight. The apparent molecular weight of each S-I arm is about 100,000 and the peak molecular weight of each polystyrene block is about 11,000. The total number of arms may vary from 6 to 100 and usually is between 6 and 40.
To this formulation several photoinitiators were added after which the compositions thus obtained were exposed to W irradiation by passing the formulation as a hot melt underneath a single Fusion D bulb lamp (F300; 300 W/inch) at a speed of 5 m/min. Of these compositions the Shear Adhesion Failure Temperature (SAFT) was measured. A value of 140 C or higher is acceptable. The results are listed in Table I.
W O 95/02640 2 1 6 ~ t ~ 5~ PCT~EPg4/02314 _ TABLE I W curing of several formulations photoinitiator (pbw) TZT X15 I651 I184 W EC SAFT (C) 1 pass 2 passes 110 >160 >160 >160 114 >160 >160 >160 3 2 10 >160 >160 151 >160 >160 >160 >160 >160 From table I it is clear that all formulations show excellent SAFT
values after 2 passes underneath the D bulb W lamp, (300 W/inch) while five formulations already give excellent SAFT values, i.e.
>160 C, after only 1 pass.
Examp;e 2 The same base formulation as used in Example 1 was employed for the evaluation of the effect on the SAFT values of the speed with which a formulation is passed underneath various W sources.
The photoinitiator used was IRGACURE 907 in an amount of 5 pbw per 100 pbw of block copolymer. When two bulb lamps were positioned in series (indicated as D+V, D+H and D+D), the exposure to the irradiation originating from the second lamp took place in air, so without applying a nitrogen flow. The results are listed in table II; the SAFT values listed are given in C.
~qo gs/02640 2 1 6 7 1 8 5 PCT~EP94/02314 TABLE II SAFT values after W curing at different speeds and with different W lamps Speed D bulb D+H bulb D+V bulb D+D bulb (m/min) l pass 2 passes 1 pass 1 pass 1 pass >160 >160 >160 >160 >160 112 >160 >160 >160 123 104 131 >160 118 105 The H and V bulb had a linear power of 300 W/inch (120 W/cm) From table II it is clear that particularly the combination of a D
bulb lamp followed by a H bulb lamp gives excellent results, even at such high speed as 20 m/min.
Characteristic adhesive properties (loop tack and peel adhesion) were also measured of same irradiated samples as listed in Tables III and IV.
TABLE III
Looptack: Influence of the lamp and speed (N/25mm) Speed D-Bulb (l lamp) D+H Bulb D+D Bulb M./Min. 1 pass 2 passes 1 pass l pass with without with without with with without *
26 24 24* 26 22 'with': means with low N2 flow - 'without': means that the samples were cured in open atmosphere (no N2 flow).
*: zippery tack W O 95/02640 2 1 6 7 1 ~ 5 PCT~EP94/02314 TABLE IV
Peel adhesion: Influence of the lamp and speed (N/25mm) Speed D-Bulb (1 lamp) D+H Bulb D+D Bulb M./Min. 1 pass 2 passes 1 pass 1 pass with without with withoutwith with without From these tables it will be appreciated that the adhesive properties are not damaged by the curing.
Example 3 The same formulation as used in Example 2 was employed and exposed to irradiation using a Fusion H bulb lamp (F300) with and without a nitrogen flow. The formulation was exposed to irradiation by passing it at different speeds once and twice underneath the H
bulb as well as by passing it once underneath two H bulb lamps positioned in series. The SAFT values (in C) were measured after each pass. The results are listed in table V.
~0 95/02640 PCT~EP94/02314 TABLE V SAFT values after W curing with and without nitrogen flow Speed 1 lamp 2 lamps (m/min) l pass 2 passes 1 pass withwithout withwithout without 88 85 107 lO1 117 From table V it can be derived that irradiation in air, so without applying a nitrogen flow, results in excellent SAFT values which are similar to, and in some cases even better than, the SAFT values obtained by applying a nitrogen flow during exposure to irradiation.
Example 4 Several photoinitiators and combinations of photoinitiators were added to the base formulation as used in Example 1. The compositions thus obtained (compositions A to G) were cured by passing them three times (lp, 2p, 3p) at a speed of 5 m/min underneath a Fusion D bulb lamp. The SAFT values, of some compositions the Holding Power at 95 C (HP 95C) and the peel adhesion 180 were determined after each pass. The results are listed in table VI.
W O 95/02640 2 ~ 5,!1 PCT~EP94/02314 _ TABLE VI
W curing of block copolymer compositions Composition A B C D E F G
Benz 5 5 10 10 5 10 lp 150 148 157133 155~160 141 SAFT (C) 2p >160 >160 158>160 >160>160 147 3p >160 >160 159>160 >160>160 151 lp >100 >100 >100>100 >100 HP 95C 2p>100 >100 >100>100 >100 3p>100 >100 >100>100 >100 Peel- lp 20 18 16 19 16 16 10 adh. 180 2p 18 20 21 21 16 15 12 (N/25mm) 3p 21 20 18 22 17 16 13 From table VI it 'can be seen that in particular the W cured adhesive compositions A to F exhibit excellent adhesive properties.
Example 5 A formulation, comprising: KRATON D-1320 X 100 phr REGALITE R 91 150 phr RF.GATRF.7. 1018 60 phr IRGACURE 907 5 phr IRGANOX 1010 1 phr was tested with irradiation from another W -lamp, the H-bulb, which substantially emits the conventional mercury spectrum.
The SAFT test results obtained have been listed in Table VII:
- ~0 95/02640 2 1 6 7 1 8 5 PCT~EP94/02314 Table VII
~ SAFT: Influence of the H-bulb lamp (C) - Speed 1 Lamp 2 Lamps M./Min. 1 pass 2 passes 1 pass with without with without without >160 >160 99 107 137 152 >160 From this table VII it will be appreciated that the N2 is not necessary and has hardly any influence on the curing efficiency of this formulation. Moreover it appeared possible to have a good curing efficiency with two passes under the H-lamp up to 15 m/min (SAFT higher than 150 CC).
The adhesive properties of these samples have also been measured and listed in Tables VIII and IX.
wo 95/02640 2 1- ~ 7 ~ ~5 PCT~EW4/02314 Table VIII
LOOPTACK: Influence of the H-bulb lamp (N/25mm) Speed 1 Lamp 2 Lamps M./Min. 1 pass 2 passes 1 pass with without with without without * - zippery tack TABLE IX
Peel adhesion: Influence of the H-bulb lamp (N/25mm) Speed 1 Lamp 2 Lamps M./Min. 1 pass 2 passes 1 pass with without with without without From the previous results it will be appreciated that the adhesive properties are not damaged by the curing whatever the curing speed or dose.
Example 6 A similar formulation (KRATON D-1320X/REGALITE
R91/REGALREZ 1018/IRGANOX 1010;100/150/60/1) was used with a - ~O 95/02640 2 1 6 7 1 8 ~ PCT~EP94/02314 combination of benzophenon and EBECRYL 7100 (or W ECRYL 7100: both trade names exist for the same product) as photoinitiator. The - samples were irradiated under a H-bulb at different speeds. The temperature resistance results (SAFT and Holding Power 95 C) have been listed in Tables X and XI:
TABLE X
SAFT: Influence of curing speed (C) Adjusted components benz. EBECRYL 5 m./min. 10 m./min. 15 m./min. 20 m./min.
1 p 2 p 1 p 2 p 1 p 2 p1 p 2 p * = zippery tack TABLE XI
HP 95 C: Influence of curing speed (h) Adjusted components benz. EBECRYL5 m./min10 m./min15 m./min 20 m./min 500 g 1 kg500 g 1 kg500 g 1 kg500 g 1 kg 10 10 1 p > 100 6 0.07 ~ 2 p > 100 61 > 100 77 15 W O 95/02640 2 1 6 7 1 85 PCT~EP94/02314 From these data it will be clear that also good curing efficiency was obtained in open air with a combination of benzophenon and tertiary amine as photoiniator.
Example 7 1. Two radiation curable block copolymer mixtures (A and B) of molecular structure (SB) B X, wherein m + n - 4, and each of m and n had an average value of about 2, wherein X represented the residue of tetrachlorosilane, were tested in an "open air"
irradiation process with two photoinitiators covered by the present application, i.e. IRGACURE 651 and IRGACURE 907 respectively.
Further details of these polymers have been listed in Table XII.
TABLE XII
Polymer A B
% PS 12.7 10.8 % vinyl 54 56 MFR 8.1 1.4 Adhesive Composition (3) (4) (5) (6) polymer 100 phr 100 ~F.~AT.F.7. 1018 63 81 2i6718~
~ ~0 95/02640 PCTAEW4/02314 The samples were cured at different speeds, under a F-300 D-bulb lamp. These adhesive formulations were irradiated in direct - cure, with low N2 flow. The results have been listed in Table XIII.
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21671~5 -~0 95/02640 PCT~EP94/02314 2. The experimental polymers A and B of the formula (SB) B X were then cured with a more powerful lamp at higher speeds, without any nitrogen flow.
The photoinitiators IRGACURE 651 and 907 were both tested in compositions, containing the same other ingredients as specified in Table XII, i.e. formulation 4 is based on A ~olymer with IRGACURE 651, formulation 5 is based on B polymer with IRGACURE
651, formulation 6 is based on B with IRGACURE 907.
All the samples were irradiated in direct curing by means of Fusion F-600 lamps.
The results have been listed in Tables XIV and XV.
TABLE XIV
Speed D-bulb I H-bulb m./min 4 5 6 1 4 5 6 I
>170 >170 >170 1>170 >170 >170 77 >170 >170 1170 >170 >170 153 >170 1166 >170 >170 105 >170 195 >170 >170 74 86 141 186 118 >170 76 8~ 95 177 92 127 I
SAFT results (C) for samples cured under one F-600 lamp W O 95/02640 2 1 ~ 7 1 ~5 PCT~EP94/02314 TABLE XV
Speed D + D bulb I D + H bulb m./min 4 5 14 5 6 >170 >170 1>170 >170 >170 >170 >170 1150 >170 >170 111 >170 1106 147 >170 82 114 186 >170 >170 110 184 >170 >170 SAFT results (C) for samples cured under a combination of F-600 lamps It will be appreciated that improved results were obtained, when using the IRGACURE 907 photoinitiators. The best results were obtained for a B polymer based formulation irradiated by a combination of D and H bulbs. In this case, SAFT results higher than 170 C could be obtained at a speed of 60 m./min! This is the highest speed which ever could be reached in radiation curing.
Holding Power (HP) at 95 C:l kg.
Only the samples which had good temperature resistance properties were selected to perform a HP 95 C test, as listed in Table XVI.
21671~5 -~VO 95/02640 PCT~EW4/02314 TABLE XVI
Speed D-bulb I H-bulb m./min 4 (h) 5 (h) 6 (h) I 4 (h) 5 (h) 6 (h) I
10 >100 >100 >100 1 >100>100 >100 >lO0 >lO0 1 0.5/12.5 >lO0 >lO0 >lO0 1 0/429.5/>lO0 >lO0 - - >lO0 1 0 >lO0 >lO0 - - - I - - 8.6 HP 95 C results of samples cured under one F-600 lamp TABLE XVII
Speed D + D bulbs I D + H bulbs m./min4 (h)5 (h) I 4 (h) 5 (h) 6 (h) I
>lO0 >lO0 1>lO0 >lO0 >lO0 >lO0 >lO0 1l9/>lO0 >lO0 >lO0 - >lO0 1 - >lO0 >lO0 - - I - >100 >100 - - I - >lO0 >lO0 HP 95 C results of samples cured under a combination of F-600 lamps Here again we can see the good temperature performance (HP95 C > lO0 h) of the experimental polymers when using IRGACURE 907 photoinitiator. IRGACURE 907 enabled the achievement of higher curing speeds.
W O 95/02640 2 1 6 7 1 8 5 PCT~EP94/02314 From the preceding examples it will be appreciated that it became possible to effectively cure in presence of oxygen without the need of a N2 flow. High curing efficiency and temperature resistance properties achievable at high speed could be reached.
Example 8 (i) Five standard radiation sensitive compositions were prepared, comprising 100 parts by weight of each of the block copolymers contA i n i ng po ly ( s tyrene) and poly(butadiene) blocks, listed in Table XVIII, 1 part by weight of the antioxidant IRGANOX lOlO and 2 parts by weight of photosensitizer IRGACURE 651.
The last block copolymer listed in the table is not according to the claimed invention and has been included as comparative example.
TABLE XVIII Polymer characteristics Block Mol.wt. Mol.wt. Total mol.wt. Molecular Poly- Vinyl-Copolymer (xlOO0) (x1000) (x1000) form styrene (1,2-add) of S of S-B content content block block A 10.7 71 276 (SB)2B2 12.7 54 B 11.2 87 339 (SB)2B2 10.8 56 C 10.7 81 222 (SB)2B2 12.5 60.5 KRATON D 13 330 (SB)3 5 21 +/- 5 Comp. 12 45 91 SBS 40 +/- 5 From the five photosensitive compositions films of 22 micron thickness were prepared from a solvent based formulation (40% in toluene) by casting.
-~O 95/02640 2 1 ~ 7 1 8 ~ PCT~EP94/02314 The films were irradiated under a Fusion D bulb lamp in 1 pass and 2 passes respectively with a speed of 5 m/min, and the gel content was analyzed.
The gel contents have been listed in Table XIX.
TABLE XIX Gel percentage after irradiation Polymer 1 pass 2 passes A 59.5 85.5 B 81.0 86.9 C 73.8 87.5 KRATON D 1116 31.7 70.4 Comp. 0.3 9.6 (ii) Photosensitive compositions were prepared from the block copolymer identified hereinbefore as A (lOO parts by weight), IRGANOX lO10 (1 part by weight) and varying amounts of photosensitizer IRGACURE 651, as listed in the Table XX.
Films of 22 micron thickness were prepared from these compositions and the films were irradiated as described under Example 8(i). The percentage.gel after irradiation was determined.
TABLE XX % gel after irradiation Composition block Copol./AO/PS 1 pass 2 passes 100/1/1 46.2 73.3 100/1/2 59.5 85.5 100/1/4 84.7 93.7
Claims (13)
1. UV-curable block copolymer composition comprising:
(a) 100 parts by weight of a multiarmed block copolymer comprising at least one polymer block A derived from a monovinyl aromatic compound and at least one polymer block B from a conjugated diene, wherein:
- the content of monovinyl aromatic compound is in the range of from 5 to 50% by weight based on the total weight of block copolymer;
- each block A has an apparent molecular weight in the range of from 1,000 to 50,000; and - each block B has an apparent molecular weight in the range of from 10,000 to 250,000; and (b) 0.5-30 parts by weight of at least one photoinitiator, characterised in thatthe multi-armed block copolymer has the structure according to any one of the general formulae:
(AB)nX, (BA)nX, (ABA)nX, (BAB)nX or (ABp(B)qX, - wherein A is a polymer block derived from a monovinyl aromatic compound, wherein B is a polymer block derived from a conjugated diene, wherein n represents an integer of 2 or higher and p and q represent an integer of 1 or higher and wherein X is the residue of the coupling agent used, that at least one photoinitiator is used, containing a carbonyl group which is directly bound to at least one aromatic ring structure;
that said composition is free from a cross-linking agent and that it is curable in an oxygen-containing atmosphere.
(a) 100 parts by weight of a multiarmed block copolymer comprising at least one polymer block A derived from a monovinyl aromatic compound and at least one polymer block B from a conjugated diene, wherein:
- the content of monovinyl aromatic compound is in the range of from 5 to 50% by weight based on the total weight of block copolymer;
- each block A has an apparent molecular weight in the range of from 1,000 to 50,000; and - each block B has an apparent molecular weight in the range of from 10,000 to 250,000; and (b) 0.5-30 parts by weight of at least one photoinitiator, characterised in thatthe multi-armed block copolymer has the structure according to any one of the general formulae:
(AB)nX, (BA)nX, (ABA)nX, (BAB)nX or (ABp(B)qX, - wherein A is a polymer block derived from a monovinyl aromatic compound, wherein B is a polymer block derived from a conjugated diene, wherein n represents an integer of 2 or higher and p and q represent an integer of 1 or higher and wherein X is the residue of the coupling agent used, that at least one photoinitiator is used, containing a carbonyl group which is directly bound to at least one aromatic ring structure;
that said composition is free from a cross-linking agent and that it is curable in an oxygen-containing atmosphere.
2. Composition according to claim 1, characterized in that a photoinitiator is used selected from the group consisting of:
(1) at least one benzophenone of the general formula (I) (I) wherein R1 to R8 independently represent hydrogen or an alkyl group having from 1 to 4 carbon atoms and wherein R7 and or R8 represent in addition alkoxy of 1 to 4 carbon atoms and wherein m has a value of 0,1 or 2, optionally in combination with at least one tertiary amine, (2) at least one sulphur-containing carbonyl compound, wherein the carbonyl group is directly bound to at least one aromatic ring, preferably of the formula II
(II) wherein R9, R10, R11 each may represent hydrogen alkyl of 1-4 carbon atoms or an alkylthio group, having 1-4 carbon atoms, and (3) mixtures of (1) and (2);
(1) at least one benzophenone of the general formula (I) (I) wherein R1 to R8 independently represent hydrogen or an alkyl group having from 1 to 4 carbon atoms and wherein R7 and or R8 represent in addition alkoxy of 1 to 4 carbon atoms and wherein m has a value of 0,1 or 2, optionally in combination with at least one tertiary amine, (2) at least one sulphur-containing carbonyl compound, wherein the carbonyl group is directly bound to at least one aromatic ring, preferably of the formula II
(II) wherein R9, R10, R11 each may represent hydrogen alkyl of 1-4 carbon atoms or an alkylthio group, having 1-4 carbon atoms, and (3) mixtures of (1) and (2);
3. Composition according to claims 1 and 2, characterized in that the-multi-armed block copolymer has a content of monovinyl aromatic compound in the range of from 5 to 25% by weight.
4. Composition according to claims 1-3, characterized in that the photoinitiatoris present in an amount of from 5 to 20 pbw per 100 pbw of block copolymer.
5. Composition according to any one of claims 1-4. Characterized in that the monovinyl aromatic compound is styrene and the conjugated diene is isoprene, 1,3-butadiene or a mixture thereof.
6. Composition according to claim 5, characterized in that the conjugated diene is isoprene.
7. Composition according to claim 1-6, wherein the photoinitiator is selected from the group consisting of benzophenone, a mixture of benzophenone and a tertiary amine, 2,4,6-trimethyl-benzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpolinopropanone-1, and mixtures thereof.
8. Composition according to claim 7, wherein the photoinitiator is 2-methyl-1-[4-methylthio) phenyl]-2-morpholinopropanone- 1 .
9. A hot melt adhesive composition the block copolymer composition according to any one of claims 1 to 8.
10. A sealant composition comprising the block copolymer composition according to any one of claims 1 to 8.
11. A coating composition comprising the block copolymer composition according to any one of claims 1 to 8.
12. A process for the curing of the compositions according to any one of claims 9-11 by exposing said compositions to UV irradiation in the presence of air.
13. A cured composition obtainable by the process of claim 12.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93202072 | 1993-07-14 | ||
| EP93202072.2 | 1993-07-14 | ||
| EP94200599.2 | 1994-03-08 | ||
| EP94200599 | 1994-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2167185A1 true CA2167185A1 (en) | 1995-01-26 |
Family
ID=26133915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002167185A Abandoned CA2167185A1 (en) | 1993-07-14 | 1994-07-12 | Uv-curable block copolymer composition |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JP3420240B2 (en) |
| CN (1) | CN1067416C (en) |
| AT (1) | ATE171972T1 (en) |
| AU (1) | AU688361B2 (en) |
| BR (1) | BR9407055A (en) |
| CA (1) | CA2167185A1 (en) |
| DE (1) | DE69413823T2 (en) |
| DK (1) | DK0708802T3 (en) |
| ES (1) | ES2122320T3 (en) |
| FI (1) | FI960137A (en) |
| MX (1) | MX9405293A (en) |
| NO (1) | NO311137B1 (en) |
| WO (1) | WO1995002640A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2324303A (en) * | 1997-04-03 | 1998-10-21 | Shell Int Research | Bituminous composition |
| US6326127B1 (en) * | 1998-12-31 | 2001-12-04 | Kraton Polymers U.S. Llc | Photo-curable polymer composition and flexographic printing plates containing the same |
| DE10049669A1 (en) | 2000-10-06 | 2002-04-11 | Tesa Ag | Process for the production of crosslinked acrylic hotmelt PSAs |
| CN1934188B (en) * | 2004-03-25 | 2010-05-05 | 克雷顿聚合物研究公司 | Thermoplastic gel compositions that can be converted into thermoset gel compositions by exposure to radiation |
| US7560503B2 (en) * | 2004-06-03 | 2009-07-14 | Kraton Polymers U.S. Llc | Gels from high molecular weight block copolymers |
| KR100834514B1 (en) * | 2005-10-17 | 2008-06-02 | 재단법인서울대학교산학협력재단 | UV curable hot melt adhesive composition and adhesive tape containing hot melt adhesive |
| CN101547989B (en) | 2006-12-07 | 2011-07-06 | 3M创新有限公司 | Blends of block copolymer and acrylic adhesives |
| KR101256553B1 (en) * | 2010-09-16 | 2013-04-23 | 주식회사 엘지화학 | Photo-sensitive resin composition, dry film solder resist, and circuit board |
| WO2017057049A1 (en) * | 2015-09-30 | 2017-04-06 | 日本ゼオン株式会社 | Block copolymer composition and hot melt adhesive composition |
| CN107674596B (en) * | 2016-08-02 | 2020-10-13 | 滕超 | Stretchable stripping adhesive tape based on ultraviolet-curable styrene block copolymer adhesive and preparation method thereof |
| CN117417726B (en) * | 2023-12-15 | 2024-03-15 | 广州鹿山新材料股份有限公司 | UV (ultraviolet) curing rubber pressure-sensitive adhesive as well as preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4556464A (en) * | 1983-04-04 | 1985-12-03 | Shell Oil Company | Endblock crosslinked block copolymer adhesive composition |
| US5270388A (en) * | 1990-04-27 | 1993-12-14 | Nippon Zeon Co., Ltd. | Shape-memorizing block copolymer composition |
| TW274086B (en) * | 1992-06-04 | 1996-04-11 | Shell Internat Res Schappej Bv |
-
1994
- 1994-07-12 MX MX9405293A patent/MX9405293A/en not_active IP Right Cessation
- 1994-07-12 AU AU74932/94A patent/AU688361B2/en not_active Ceased
- 1994-07-12 AT AT94924758T patent/ATE171972T1/en not_active IP Right Cessation
- 1994-07-12 DK DK94924758T patent/DK0708802T3/en active
- 1994-07-12 BR BR9407055A patent/BR9407055A/en not_active IP Right Cessation
- 1994-07-12 ES ES94924758T patent/ES2122320T3/en not_active Expired - Lifetime
- 1994-07-12 WO PCT/EP1994/002314 patent/WO1995002640A1/en active IP Right Grant
- 1994-07-12 JP JP50434695A patent/JP3420240B2/en not_active Expired - Lifetime
- 1994-07-12 CN CN94192754A patent/CN1067416C/en not_active Expired - Lifetime
- 1994-07-12 CA CA002167185A patent/CA2167185A1/en not_active Abandoned
- 1994-07-12 DE DE69413823T patent/DE69413823T2/en not_active Expired - Lifetime
-
1996
- 1996-01-11 NO NO19960130A patent/NO311137B1/en not_active IP Right Cessation
- 1996-01-11 FI FI960137A patent/FI960137A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR9407055A (en) | 1996-08-13 |
| NO311137B1 (en) | 2001-10-15 |
| AU688361B2 (en) | 1998-03-12 |
| FI960137A0 (en) | 1996-01-11 |
| DE69413823T2 (en) | 1999-03-18 |
| WO1995002640A1 (en) | 1995-01-26 |
| CN1127008A (en) | 1996-07-17 |
| FI960137A (en) | 1996-01-11 |
| ATE171972T1 (en) | 1998-10-15 |
| DK0708802T3 (en) | 1999-06-21 |
| AU7493294A (en) | 1995-02-13 |
| MX9405293A (en) | 1995-01-31 |
| JPH09500156A (en) | 1997-01-07 |
| NO960130D0 (en) | 1996-01-11 |
| JP3420240B2 (en) | 2003-06-23 |
| ES2122320T3 (en) | 1998-12-16 |
| CN1067416C (en) | 2001-06-20 |
| NO960130L (en) | 1996-03-12 |
| DE69413823D1 (en) | 1998-11-12 |
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