Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
  • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
  • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
  • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/06—Fibrous reinforcements only
  • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
  • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
  • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
  • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
  • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B2038/0052—Other operations not otherwise provided for
  • B32B2038/0076—Curing, vulcanising, cross-linking
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/08—Reinforcements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/74—Partially cured
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2310/00—Treatment by energy or chemical effects
  • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
  • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

• the invention relates to fiber-reinforced laminates having at least two layers.
• This object is achieved through the use of binders, at least of one outer layer, which are curable by irradiation with high-energy light.
• the invention accordingly provides fiber-reinforced laminates having at least two layers wherein an outer layer A′ containing a polymer A containing allyl groups, acrylic groups and/or methacrylic groups and being curable by high-energy radiation and an adjacent layer comprises reinforcing fibers and a curable composition B′ comprising a polymer B selected from systems polymerizable free-radically (B1) and by irradiation with high-energy light (B2).
• the invention further provides a process for producing cured laminates which comprises the steps of (1) producing a cured polymer layer A′ from a polymer A by irradiation with high-energy light and (2) applying a further layer to the layer A′ produced in step (1), the further layer comprising reinforcing fibers and a curable composition B′ which originates by free-radical polymerization from a free-radically polymerizable system B1 and/or by irradiation of a system B2 with high-energy light.
• the invention likewise provides a process for producing shaped laminates which comprises bringing the incompletely cured laminates into the desired shape under the action of heat and pressure and subsequently curing them.
• a molding or a surface of a smooth substrate is coated with a layer Z which has an antiadhesive effect, after which in step (1) this layer is coated with a composition comprising a substance A polymerizable by irradiation with high-energy light, the substance A being polymerized by irradiation and so cured, in step (2) the free surface of this layer is coated with a curable composition B′ comprising a polymer B selected from systems polymerizable free-radically (B1) and by irradiation with high-energy light (B2) and reinforcing fibers, and then the curable composition B′ is at least partly cured, and then detached from the surface or molding for ultimate curing.
• a curable composition B′ comprising a polymer B selected from systems polymerizable free-radically (B1) and by irradiation with high-energy light (B2) and reinforcing fibers
• the polymers A and B2 are selected independently of one another from epoxy acrylates, urethane acrylates, melamine acrylates, polyether acrylates, polyester acrylates, the corresponding methacrylates, and esters of other olefinically unsaturated acids, and polyesters or polyethers both containing allyl groups, and also mixtures thereof.
• Epoxy acrylates are reaction products of epoxy resins C with carboxyl group-containing olefinically unsaturated compounds G.
• epoxy resins C it is possible to use the glycidyl ethers of dihydroxyaromatics such as resorcinol, dihydroxybenzophenone, dihydroxydiphenylsulfone, and, preferably, bisphenol A and bisphenol F; it is also possible to use glycidyl ethers of aliphatic diols such as butanediol and hexanediol, and also epoxy resins of higher molar mass, which are obtainable preferentially from bisphenol A and/or bisphenol F by the Taffy process (reaction of these bisphenols with epichlorohydrin) and by the so-called advancement reaction (reaction of bisphenol diglycidyl ethers with the free bisphenols). It is also possible to use epoxy resins based on novolaks and epoxidized oils.
• Carboxyl group-containing olefinically unsaturated compounds G which can be used here are in particular acrylic acid and methacrylic acid, but also crotonic acid, vinylacetic acid, and the monoesters of olefinically unsaturated dicarboxylic acids, such as monomethyl maleate, monomethyl fumarate, and the monoalkyl esters of citraconic, itaconic, and mesaconic acids. Preference is given to the first-mentioned acrylic acid and methacrylic acid.
• Urethane acrylates are reaction products D(E)F of polyfunctional isocyanates D and hydroxyl group-containing olefinically unsaturated compounds F and also, where appropriate, polyfunctional aliphatic alcohols E.
• the polyfunctional isocyanates D are at least difunctional and can be selected from aromatic and aliphatic linear, cyclic, and branched isocyanates, especially diisocyanates. Preference is given to diisocyanates, where it is possible for up to 5% of their mass to be replaced by isocyanates having a functionality of three or more.
• the diisocyanates preferably possess the formula Q(NCO) 2 , where Q is a hydrocarbon radical having 4 to 40 carbon atoms, in particular 4 to 20 carbon atoms, and preferably an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, an aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
• Q is a hydrocarbon radical having 4 to 40 carbon atoms, in particular 4 to 20 carbon atoms, and preferably an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, an aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
• diisocyanates for use with preference are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4′-diisocyanatodicyclohexylmethane, 2,2-bis(4-isocyanatocyclohexyl)propane, 1,4-diisocyanatobenzene, 2,4- or 2,6-diisocyanatotoluene and mixtures of these isomers, 4,4′- or 2,4′-diisocyanatodiphenylmethane, 2,2-bis(4-isocyanatophenyl)propane, p-xylylene diisocyanate, and ⁇ , ⁇ , ⁇ ′, ⁇ ′
• polyisocyanates In addition to these simple polyisocyanates, also those are suitable which contain heteroatoms in the radical linking the isocyanate groups. Examples of such are polyisocyanates containing carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea groups or biuret groups. For further suitable polyisocyanates reference may be made, for example, to DE-A 29 28 552.
• the polyfunctional aliphatic alcohols E used if desired have at least two hydroxyl groups per molecule and 2 to 150 carbon atoms, preferably 3 to 40, and in particular 4 to 20 carbon atoms. They can be linear, branched or cyclic and can also contain heteroatoms, such as ether bonds, ester bonds or secondary or tertiary amine bonds, in the molecule.
• Compounds of this kind are ether alcohols or polyether alcohols such as polyethylene glycol, polypropylene glycol, mixtures thereof and copolymers and polyoxybutylenediol (“poly-THF”), and also polyester alcohols and amino alcohols.
• the hydroxyl group-containing ethylenically unsaturated compounds F are aliphatic mono- or polyunsaturated compounds having 3 to 20 carbon atoms and at least one hydroxyl group. Particular preference is given to allyl alcohol and to the monoesters of dihydric alcohols F1 with the abovementioned olefinically unsaturated acids G, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, 2- and 3-hydroxypropyl (meth)acrylate, 1-hydroxy-2-propyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate, esters of trihydric or higher polyhydric alcohols with an acid containing olefinically unsaturated groups, with at least one hydroxyl group remaining unesterified, examples being trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and the acrylates and
• Melamine acrylates are reaction products of hydroxyl group-containing olefinically unsaturated compounds F with alkylolmelamines obtained by reacting melamine and aldehydes, especially formaldehyde. Melamine acrylates are prepared in particular by transetherification of hexamethoxymethylmelamine with the compounds F. It is also possible to etherify the compounds F directly with methylolated melamine, for example, hexamethylolmelamine; this process, however, is not carried out on the industrial scale.
• Polyether acrylates are esters of polyalkylene glycols having degrees of polymerization of preferably from 4 to 100, especially polypropylene glycol, poly(oxy-1,4-butylene) glycol and mixed copolymers having oxyethylene and oxypropylene units, with the olefinically unsaturated acids specified under G; they are normally prepared by transesterification with ethyl (meth)acrylate or similar esters.
• Polyester acrylates are esterification products of olefinically unsaturated acids G with hydroxyl group-containing polyols or polyesters or esterification products of hydroxyl group-containing olefinically unsaturated compounds F with acid groups of a polyester.
• the polyesters are normally derived from linear or branched aliphatic polyols having two or more hydroxyl groups and from 2 to 20 carbon atoms, such as glycol, neopentylglycol, butanediol, 1,6-hexanediol, diethylene and triethylene glycol, trimethylolpropane, pentaerythritol, and sorbitol, and aliphatic linear or cyclic dicarboxylic acids such as adipic acid and cyclohexanedicarboxylic acid, the hydroxyl group-containing polyether polyols based on ethylene oxide and propylene oxide or mixtures thereof and on polytetrahydrofuran, and also on ethoxylated and/or propoxylated polyhydric alcohols, such as those mentioned above.
• linear or branched aliphatic polyols having two or more hydroxyl groups and from 2 to 20 carbon atoms
• glycol neopent
• acrylates are referred to above, in the context of the disclosure these acrylates also of course include the corresponding methacrylates and the esters of the other acids mentioned under G.
• Allyl group-containing compounds are ethers or esters or mixed ether-esters of allyl alcohol with polyhydric alcohols or their ethoxylation and/or propoxylation products or allyl esters of the abovementioned aliphatic carboxyl group-containing polyesters.
• the unsaturated polyesters B1 are styrene-free polyesters based on allyl ethers of polyhydric alcohols, the number of allyl groups always being less by one than the number of hydroxyl groups of the unetherified alcohol, aliphatic linear, branched or cyclic diols having 2 to 20 carbon atoms, olefinically unsaturated dicarboxylic acids having 4 to 20 carbon atoms, such as fumaric acid in particular, and small amounts of monohydric alcohols, especially benzyl alcohol, the amount of the latter being such that crosslinking through the polyunsaturated compounds is kept within limits.
• Suitable reinforcing fibers are glass fibers in particular but also carbon fibers, aramid fibers, particularly those of the so-called high-modulus polymers such as poly-para-phenyleneterephthalamide ®Kevlar or ®Twaron) and copolymers (e.g., ®Teijin HM50) containing more than 30% of units derived from terephthalic acid and para-phenylenediamine, and also fibers of liquid-crystalline polyesters and fibers of ultrahigh molar mass polyethylene (e.g., ®Dyneema).
• aramid fibers particularly those of the so-called high-modulus polymers such as poly-para-phenyleneterephthalamide ®Kevlar or ®Twaron
• copolymers e.g., ®Teijin HM50
• liquid-crystalline polyesters and fibers of ultrahigh molar mass polyethylene e.g., ®Dyneema
• antiadhesive layer Z it is possible to use a standard release agent (for example, waxes, silicone-modified waxes, fatty acid amide waxes, salts of long-chain fatty acids like zinc stearate, polyvinyl alcohol, fluorinated polymers, and natural phospholipids such as soya lecithin).
• a standard release agent for example, waxes, silicone-modified waxes, fatty acid amide waxes, salts of long-chain fatty acids like zinc stearate, polyvinyl alcohol, fluorinated polymers, and natural phospholipids such as soya lecithin).
• the laminates of the invention can be employed in all applications where use has been made to date, for example, of laminates comprising glass fiber mats with unsaturated polyesters with a gel coat surface.
• UV-curable coatings 2.1 and 2.2 according to table 3 were applied to glass plates as described in example 1 coated with release agent as above.
• the coatings were cured under 2 mercury lamps and 2 gallium-doped mercury lamps, each with a power of 80 W/cm, at a belt speed of 5 m/min from a distance of 10 cm, and after curing were detached from the glass plates and joined to a UV-curable laminating layer.
• This layer consisted of a 10 ⁇ 20 cm 2 glass fiber mat (approximately 5 g/m 2 ) to which approximately 20 g of the UV laminating materials 2.3 and 2.4, in accordance with the indication in table 3, have been applied.
• This molding i.e. the veneer/laminate composite
• a UV clearcoat material in accordance with coating 3.3 (see table 5), the clearcoat material being applied in one instance in 2 coats and in another instance with 3 coats, the wet thickness of each coat being 200 ⁇ m.
• the coating was cured again by exposure to 2 mercury lamps each with a power of 80 W/cm at a belt speed of 10 m/min.
• the surface coated with the UV clearcoat material and cured matches a high-build polyester coating that can be completed within a short time.
• a high-build polyester coating requires at least 6 or 7 applications each at a rate of approximately 250 g/m 2 , possibly with subsequent sanding/polishing/buffing; the overall layer thickness at the end of the processing operation is in that case about 700 to 800 ⁇ m; the coating operation takes about 4 to 5 hours, and finishing by sanding and polishing cannot take place until 72 h after the coating operation.
• styrene-containing unsaturated polyester resins with the conventional free-radical curing by means of cobalt salts and peroxides can be replaced by styrene-free UV-curable systems.
• the advantage of these systems is the absence of styrene and the increased reactivity of the UV-curable system and consequent higher productivity.
• Veneer/laminate composites can be produced in one work step using the UV technology.
• the use of a UV clearcoat system to replace UP coating material produces a distinct increase in productivity owing to more rapid curing.

Landscapes

• Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Composite Materials (AREA)
• Mechanical Engineering (AREA)
• Electromagnetism (AREA)
• Toxicology (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Thermal Sciences (AREA)
• Laminated Bodies (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=32111258

Family Applications (2)

Family Applications After (1)

Country Status (3)

Cited By (2)

Families Citing this family (5)

Citations (4)

Family Cites Families (14)

• 2002
  • 2002-11-15 AT AT0172502A patent/AT502316A1/de not_active Application Discontinuation
• 2003
  • 2003-11-06 EP EP20030025507 patent/EP1419874A1/de not_active Withdrawn
  • 2003-11-12 US US10/706,111 patent/US20040096660A1/en not_active Abandoned
• 2005
  • 2005-11-04 US US11/266,946 patent/US20060057397A1/en not_active Abandoned

Patent Citations (4)

Also Published As

Similar Documents

Legal Events