Radiation-curable composition for composite materials

Abstract

(A) At least 20% by weight of compound A containing at least two ethylenically unsaturated moieties and a structural moiety; (B) at least 20% by weight of compound B containing at least two ethylenically unsaturated moieties and an alicyclic structure or a heterocyclic aliphatic structure; (C) 1 to 40% by weight of compound C, which essentially contains one ethylenically unsaturated moiety and has a viscosity of less than 100 mPa·s, preferably less than 50 mPa·s, more preferably less than 25 mPa·s when measured at 25 °C, and is different from compounds A and B; and (D) 0 to 20% by weight of compound D containing at least one ethylenically unsaturated moiety and different from compounds A, B, and C, a radiation and / or thermosetting composition (I) for a composite material, wherein the total of compounds B and A has a content of 60 to 99% by weight in light of the total content of compounds A, B, C, and optionally D, a thermosetting composition (I).

Description

Technical Field

[0001] The present invention relates to the field of actinic radiation and / or thermosetting compositions for composite materials, composite materials and filling materials containing such compositions, and methods of coating filling materials.

Background Art

[0002] A composite or composite material is a combination of two or more immiscible materials, typically including a plastic or resin matrix and a filler material, whereby the resin holds the filler materials together and forms a continuous phase for the structure and the bonding of the filler materials. Composites can have various shapes and mechanical properties depending on their application. Their applications are numerous and can be used, for example, in automobiles, aerospace, transportation, construction, and electronic devices. Composites are often used not only for pipes such as geothermal pipes but also for making pipes for offshore and onshore applications.

[0003] State-of-the-art composite manufacturing techniques are often not cost-effective due to long curing times with heating and cooling cycles. For this reason, their use in high-volume applications is hindered. When radiation curing is used in composite manufacturing, the curing occurs very rapidly and at low temperatures, so this cycle time can be significantly shortened. For this reason, it is suitable for high-volume production of composite materials. UV light-curable compositions have been developed that can form a resin matrix for filler materials. UV-light has the advantage that curing is extremely fast and significantly improves the manufacturing process.

[0004] A UV light-curable composition in which the composite composition contains a resin containing isosorbide diacrylate is described in International Publication No. WO 2014 / 191308. This type of composition has the drawback of providing a rather hard composite when cured.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Many applications require composite materials that have a certain degree of flexibility, can withstand a certain amount of stress, and have a certain amount of toughness. It is difficult to obtain a good balance of these properties.

Means for Solving the Problems

[0006] This time, the inventor has surprisingly found a composition that at least partially overcomes the above problems by providing the actinic ray and / or thermosetting composition (I) according to claim 1. Therefore, the first aspect of the present invention relates to an actinic ray and / or thermosetting composition (I) for a composite material, which is (A) at least 20% by weight of compound A containing a structural moiety selected from the group consisting of at least two ethylenically unsaturated moieties and a polyalkylene glycol, such as polyethylene glycol; polypropylene glycol; polycaprolactone; polybutadiene or its hydrogenated or partially hydrogenated form; polyisoprene or its hydrogenated or partially hydrogenated form; and a polyester derivable from a polyol and a dicarboxylic acid; (B) at least 20% by weight of compound B containing at least two ethylenically unsaturated moieties and an alicyclic structure or a heterocyclic aliphatic structure; (C) 1 to 40% by weight of compound C, which is essentially one ethylenically unsaturated moiety and has a viscosity of less than 100 mPa·s, preferably less than 50 mPa·s, and more preferably less than 25 mPa·s when measured at 25 °C, different from compounds A and B; and (D) 0 to 20% by weight of compound D containing at least one ethylenically unsaturated moiety different from compounds A, B, and C and the total of compounds B and A has a content of 60 to 99% by weight relative to the total content of compounds A, B, C, and optionally D; the curable composition (I) has a glass transition temperature (Tg) of at least 90 °C according to the standard test method ASTM E1640 using dynamic mechanical analysis after curing.

[0007] Such compositions can be used in composite materials and have been found to have one or more of the following advantages: · May be suitable for high-volume applications in high-speed production · Can be used to form a wide variety of composite articles · May be suitable for obtaining composite articles with little shrinkage upon curing, thereby preventing warping and / or poor part fitting · May have low toxicity; · Do not contain bisphenol A; · Do not contain styrene; · Composition (I) may have a low viscosity and facilitate use in liquid composite manufacturing processes; · Composition (I) may have a good pot life even at room temperature; · The storage cost of composition (I) may be low.

[0008] In addition, such compositions provide composite materials that, after curing with actinic radiation and / or heat, still have high thermal resistance with some flexibility, i.e., the composition provides a coating with a sufficiently high glass transition temperature and good elongation properties, which can withstand a high ultimate flexural strain. Compositions with a high Tg are usually hard and brittle. Surprisingly, it has been found that the compositions of the present invention can be flexible after curing yet still have a high Tg. In some cases, they even provide good saltwater resistance.

[0009] Accordingly, the present invention also relates, in a second aspect, to a composite material comprising the curable composition (I) and the filler material (II) of the first aspect.

[0010] In a third aspect, the present invention relates to a method of making a composite material, which comprises · contacting a filler material with the curable composition (I) of the first aspect; · curing the curable composition (I) in contact with the filler material and includes.

[0011] This may exhibit one or more of the following advantages: · Fast; · Can be carried out at low temperatures; · Can be carried out as required, thereby facilitating handling in industrial production; · May be cost-effective; · Can be used in high-capacity applications; · May require low energy consumption as there is no need to heat it in one case.

Mode for Carrying Out the Invention

[0012] The first aspect is: (A) At least 20% by weight of compound A containing a structural part selected from the group consisting of at least two ethylenically unsaturated parts and polyalkylene glycol; polycaprolactone; polybutadiene or its hydrogenated or partially hydrogenated form; polyisoprene or its hydrogenated or partially hydrogenated form; polyester derivable from polyol and dicarboxylic acid; (B) At least 20% by weight of compound B containing at least two ethylenically unsaturated parts and an alicyclic structure or a heterocyclic aliphatic structure; (C) 1 to 40% by weight of compound C, which essentially contains one ethylenically unsaturated part and has a viscosity of less than 100 mPa·s, preferably less than 50 mPa·s, and even more preferably less than 25 mPa·s when measured at 25 °C, and is different from compounds A and B; (D) 0 to 20% by weight of compound D containing at least one ethylenically unsaturated part and different from compounds A, B, and C A chemical radiation and / or thermosetting composition (I) for a composite material, comprising: The total of compounds B and A has a content of 60 to 99% by weight in light of the total content of compounds A, B, C, and optionally D; Regarding composition (I), having a glass transition temperature (Tg) of at least 90 °C according to the standard test method ASTM E1640 using dynamic mechanical analysis after curing.

[0013] It has been found that such compositions, after curing, provide a material having an ultimate tensile elongation greater than 3%, preferably greater than 5%. Here, the tensile elongation is measured according to the standard test method ASTM D638 for determining uniaxial stress-strain (tensile) properties. Such compositions are suitable for composite materials that require a certain amount of formability, such as (spoolable) pipes, (printed) sleeves, and windmill gears. The composition (I) according to the first aspect can also be used to repair articles made of composite materials.

[0014] Composition (I) has a glass transition temperature of 90 °C or higher, preferably 100 °C or higher, after curing, where Tg is measured according to the standard test method ASTM E1640 using dynamic mechanical analysis.

[0015] Also, such compositions provide a material with very high flexural bending properties after curing and have an ultimate flexural strain greater than 5%, preferably greater than 6%, when measured according to the standard test method ASTM D790 in which a three-point bending test is performed.

[0016] Accordingly, in one embodiment, the curable composition (I) has an ultimate tensile elongation greater than 3% and an ultimate flexural strain greater than 5%.

[0017] As used herein, the term "ethylenically unsaturated moiety" means a moiety containing a polymerizable ethylenically unsaturated group. A polymerizable ethylenically unsaturated group means a carbon-carbon double bond that can ultimately undergo radical polymerization in the presence of a photoinitiator under the influence of an initiator and / or irradiation. Polymerizable ethylenically unsaturated groups are generally selected from (meth)acrylic groups. In the present invention, it should be understood that the term "(meth)acrylic" encompasses both acrylic and methacrylic groups present in a compound either separately or as a mixture thereof.

[0018] As used herein, "chemically curable composition" means a composition that can be cured at least in part by electromagnetic radiation, such as near-infrared, visible light, UV light, or X-rays, particularly UV light, or particle beams, such as electron beams. Chemically curable radiation can occur in the presence of a photoinitiator (system). Preferably, the composition of the first aspect cures completely after exposure to chemically curable radiation.

[0019] As used herein, "composite material" refers to a composite material composed of a plastic or resin matrix, where the resin matrix holds reinforcing components. The reinforcing components in the composite material increase the rigidity and tensile strength of the composite.

[0020] UV light radiation means irradiation by an ultraviolet light source, such as a high or low pressure mercury lamp, cold cathode tube, xenon lamp, black light, ultraviolet laser, and flashlight, as well as an LED light source. Generally, the wavelength of the UV light source is 240 - 405 nm.

[0021] Radiation using an LED light source means irradiation by a light emitting diode source using a semiconductor light source. Generally, wavelengths of 365, 385, 395, or 405 nm are used.

[0022] As used herein, "thermosetting composition" is a composition that can be cured by polymerization initiated by a free radical generator, such as peroxides and azo-type initiators. Peroxide initiators include diacyl peroxides, hydroperoxides, ketone peroxides, peroxy esters, peroxy ketals, dialkyl peroxides, alkyl peresters, and percarbonates, which are used alone or in combination with a redox system. Examples of these peroxides include methyl ethyl ketone peroxide (MEKP), methyl isobutyl ketone peroxide (MIBK), benzoyl peroxide (BPO), and cumene hydroperoxide (CHP). Combinations of two or more peroxides may be used to cure the resin. Azo-type initiators include azobisisobutyronitrile (AIBN) and related compounds.

[0023] Free radical reactions can be accelerated by the use of metal carboxylates such as cobalt naphthenate and cobalt octanoate. Zinc, iron, vanadium, potassium and other metal complexes can also be used in this process. Nitrogen-containing compounds, such as aniline, various amides, and derivatives of aromatic and aliphatic amines, may be used to improve curing. In the absence of such accelerators, curing can be caused, for example, by heating to a temperature higher than 60°C. When accelerators are present, curing can occur at room temperature (i.e., about 20°C), or by heating at a higher temperature, such as 30°C or higher.

[0024] "For composite materials" means "suitable for composite materials".

[0025] Compound A contains structural moieties selected from the group consisting of at least two ethylenically unsaturated moieties and polyalkylene glycol; polycaprolactone; polybutadiene or its hydrogenated or partially hydrogenated form; polyisoprene or its hydrogenated or partially hydrogenated form; or a polyester derivable from a polyol and a dicarboxylic acid.

[0026] In one embodiment, the structural moiety is derived from a compound having a Tg of less than 0°C, preferably less than -20°C, more preferably less than -30°C, and even more preferably less than -40°C.

[0027] Preferably, the Tg of compound A, when homopolymerized, is higher than 0°C, more preferably higher than 10°C, and even more preferably higher than 30°C. Preferably, the Tg is lower than 80°C.

[0028] In one embodiment, the polyester structural moiety is · The condensation reaction of a linear aliphatic dicarboxylic acid having 4 to 14 carbon atoms with an aliphatic or alicyclic polyol, preferably an aliphatic diol or an alicyclic diol; · The condensation reaction of a dimerized fatty acid compound with an aliphatic or alicyclic diol; or · The condensation reaction of the dimerized fatty alcohol compound with an aliphatic diacid compound can be derived from.

[0029] The polyalkylene glycol moiety preferably has the structure -((CH2)nO)x- or -(CH2CH(CH3)O)x-; (where n is an integer from 2 to 5 and x is an integer from 5 to 20). Preferred examples are polyethylene glycol (Tg about -67 °C), bio-based polypropylene diol (also called poly(trimethylene glycol) or poly(1,3-propanediol)) (Tg about -77 °C); polypropylene glycol (Tg about -74 °C); poly-tetrahydrofuran (also called poly-tetramethylene oxide) (Tg about -86 °C) moieties;

[0030] The polycaprolactone moiety preferably has the structure -(C(C=O)(CH2)uO)t-; (where u is an integer from 3 to 5 and t is an integer from 4 to 20. Typically this moiety is derived from polycaprolactone having a Tg of about -66 °C).

[0031] The polybutadiene moiety preferably has the structure -(CH2-CH(CH=CH2)p-(CH2-CH=CH-CH2)q-; (where the sum of p and q is an integer from 10 to 100, p≥0, q≥0; or its hydrogenated or partially hydrogenated form). Preferred examples are poly(1,2-butadiene) (Tg about -13 °C) and poly(1,4-butadiene) (Tg about -105 °C) moieties.

[0032] The polyisoprene moiety preferably has the structure -(CH2-C(CH3)=CH-CH2)r-, (where r is an integer from 10 to 100, or its hydrogenated or partially hydrogenated form).;

[0033] The polyester moiety preferably has the structure -(O(C=O)-R’-(C=O)O-R”-)n- (wherein, R’ is a saturated straight-chain alkyl having 2 to 14 carbon atoms, R” is a saturated aliphatic or alicyclic alkyl, and n is an integer of 3 to 20; · wherein, R’ is a dimerized fatty acid residue; R” is a saturated aliphatic or alicyclic alkyl; n is an integer of 3 to 20; or · wherein, R’ is an aliphatic diacid residue; R” is a dimerized fatty diol residue; n is an integer of 3 to 20).

[0034] Examples of polyester moieties where R’ is a saturated straight-chain alkyl having 4 to 14 carbon atoms and R” is a saturated aliphatic or alicyclic alkyl are moieties derived from poly(ethylene adipate) (Tg about -44 °C), poly(1,4-butylene adipate) (Tg about -68 °C).

[0035] Examples of polyester moieties where R’ is a dimerized fatty acid residue; R” is a saturated aliphatic or alicyclic alkyl; and n is an integer of 3 to 20; or where R’ is an aliphatic diacid residue; R” is a dimerized fatty diol residue; and n is an integer of 3 to 20 are polyesters derived from the Pripol™ or Priplast™ range commercially available from Croda.

[0036] Compound A is present in an amount of at least 20% by weight relative to the total amount of composition (I) comprising compound A, B, C and optionally compound D.

[0037] Preferably, compound A contains at least two (meth)acrylate groups and at most 8, more preferably at most 6 (meth)acrylate groups.

[0038] In one embodiment, the weight-average molecular weight of the structural moiety is from 200 to 10,000, more preferably from 400 to 5000.

[0039] In a preferred embodiment, Compound A is a polyester di- or tri-(meth)acrylate or a polyurethane di- or tri-(meth)acrylate; wherein the polyester (meth)acrylate is a reaction product of (meth)acrylic acid and a polyol containing the structural moiety defined above; and the polyurethane (meth)acrylate is a reaction product of a mono- or poly-hydroxy (meth)acrylate, a mono- or poly-isocyanate and a compound containing the structural moiety defined above. A person skilled in the art can prepare such types of polyester or polyurethane.

[0040] Preferred examples of Compound A are di- or tri-(meth)acrylate compounds containing structural moieties based on poly(tetramethylene oxide), poly(propylene oxide), poly(ethylene oxide) moieties, polyester moieties formed as the condensation reaction product of C4-C20 linear alkyldicarboxylic acids and aliphatic or cycloaliphatic diol compounds, polyester moieties formed by the condensation reaction of dimerized fatty acids and aliphatic or cycloaliphatic diols or polyester moieties formed by the condensation reaction of dimer fatty diols and aliphatic dicarboxylic acid compounds.

[0041] Examples of such compounds include urethane di- or tri-(meth)acrylate compounds or polyester di- or tri-(meth)acrylate compounds containing these structural moieties.

[0042] Compound B contains at least two ethylenically unsaturated moieties, preferably (meth)acrylate groups, and an alicyclic structure or a heterocyclic aliphatic structure.

[0043] In one preferred embodiment, Compound B does not contain the structural moiety of Compound A.

[0044] Compound B contains at least two ethylenically unsaturated moieties and preferably no more than 8, more preferably no more than 6 ethylenically unsaturated moieties.

[0045] Compound B further has a cyclic structure that is alicyclic or heterocyclic aliphatic. The structure may also be polycyclic. "Alicyclic structure" means an aliphatic hydrocarbon containing at least one ring structure. "Heterocyclic aliphatic structure" means a cyclic structure in which the cyclic structure has atoms of at least two different elements as ring members (singular or plural) of the ring(s). The atoms are preferably carbon, amine, oxygen and / or sulfur. The ethylenically unsaturated moiety of compound B may be bonded to the cyclic structure, or there may be a linker between the ethylenically unsaturated moiety and the cyclic structure(s). The cyclic structure(s) may further have a functional group. Compound B does not contain an aromatic ring structure.

[0046] Preferred examples of compound B are tricyclodecanedimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, isosorbide-based poly(meth)acrylate, such as isosorbide di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate.

[0047] Composition (I) contains at least 20% by weight of compound A, preferably 20% to 79% by weight, more preferably 20% to 40% by weight of compound A.

[0048] Composition (I) contains at least 20% by weight of compound B, preferably 20% to 79% by weight, more preferably 20% to 50% by weight of compound B.

[0049] The total of compound B and A has a content of 60 to 99% by weight in light of the total content of compounds A, B, C and optionally D.

[0050] Composition (I) further contains 1 to 40% by weight of compound C, which is different from compounds A and B, essentially contains one ethylenically unsaturated moiety, and has a viscosity of less than 100 mPa·s, preferably less than 50 mPa·s, even more preferably less than 25 mPa·s when measured at 25 °C.

[0051] Preferably, essentially one ethylenically unsaturated moiety is a (meth)acrylate functional group. Preferably, compound C is added to composition (I) in an amount such that the viscosity of composition (I) measured at 25°C is 2500 or less, preferably less than 1800, more preferably less than 1500, preferably less than 1000 mPa·s. The viscosity is preferably more than 100 mPa·s, more preferably more than 200 mPa·s when measured at 25°C. The low viscosity facilitates contact with the filling material. The application temperature, i.e., the temperature at which composition (I) is brought into contact with the filling material to obtain the composite, can be room temperature, but can also be a higher temperature.

[0052] Accordingly, in one embodiment, the curable composition (I) has a viscosity of 2500 or less, preferably less than 1800, more preferably less than 1500 mPa·s when measured at 25°C.

[0053] Mono(meth)acrylate-functional compounds (C) having a low viscosity are well known in the art and essentially contain one radiation-curable (meth)acrylate group.

[0054] The mono(meth)acrylate-functional compound (C) is a monofunctional (meth)acrylate monomer. Preferably, the (meth)acrylate-functional monomer compound C used has a number average molecular weight (Mn) in the average range of 100 to 1000 Daltons, more preferably 120 to 800 Daltons, and most preferably 120 to 500 Daltons. Typically, the weight average molecular weight (MW) is at most 1000 Daltons.

[0055] Preferably, the Tg of the mono(meth)acrylate-functional compound (C) when homopolymerized is preferably at least 40°C, more preferably higher than 50°C, and even more preferably higher than 60°C.

[0056] Examples of suitable mono(meth)acrylate functional monomers are alkyl (meth)acrylates represented by the formula CH2=C(R1)COOCzH2z+1, where R1 is a hydrogen atom or a methyl group, z is 1, and CzH2z+1 may have a straight-chain or branched-chain structure.Suitable examples of suitable mono(meth)acrylate functional monomers include, but are not limited to: beta-carboxyethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, octyl-decyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxy (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopropylidene glycerol (meth)acrylate, isobornyl (meth)acrylate (IBO(M)A), 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acryloylmorpholine, phenyl glycidyl ether (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, n-butylacryloyloxyethyl carbamate, glycerol (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, reaction products of (meth)acrylic acid with aliphatic carboxylic acids such as glycidyl esters of neodecanoic acid and mixtures thereof; styrene; norbornyl (meth)acrylate; dicyclopentadienyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate are included.

[0057] Preferably, the monomer may also be biobased. Compounds such as IBO(M)A can also be partially biobased compounds, thereby increasing the biobased content of the reacted product.

[0058] Since styrene is considered a harmful compound, it is preferably not used.

[0059] Composition (I) may optionally contain a compound D containing at least one ethylenically unsaturated moiety in an amount of 0 to 20% by weight, which is different from compounds A, B, and C. Compound D is preferably a (meth)acrylate-functional compound. Examples of such compounds can vary widely and, in addition to radiation-curable moieties, include various backbone structures such as, but not limited to, urethane, epoxy, polyester, polyether, or acrylic functionality. For example, compound D can be selected from polyester (meth)acrylate oligomers, urethane (meth)acrylate oligomers, alkoxylated (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, aminated (meth)acrylate oligomers, (meth)acrylate-functionalized (meth)acrylic oligomers, (meth)acrylic (co)polymer oligomers, or combinations thereof.

[0060] Composition (I) has a Tg of at least 90 °C. The types and concentrations of compounds A, B, C, and optionally D according to the invention are selected such that the Tg of composition (I) is at least 90 °C.

[0061] In particular, when selecting the Tg of compounds C and / or D, it is important that their Tg in the polymerized form and their concentration be considered such that the Tg of composition (I) is at least 90 °C. One skilled in the art can select the compounds and concentrations such that the composition has a Tg of at least 90 °C and maintains good properties such as the targeted viscosity. The targeted viscosity is preferably not too high at the temperature at which the composition is applied. Preferably, the Tg of compound D, when homopolymerized, is at least 20 °C, more preferably higher than 30 °C, and even more preferably higher than 50 °C. Compound D can have a lower Tg, but in that case it is preferred to use a lower concentration.

[0062] In a plurality of embodiments, the composition may include a photoinitiator. Curing of the composition can be carried out with or without using a photoinitiator. Typically, the compositions of the present invention include at least one photoinitiator. Any photoinitiator or mixture thereof capable of generating free radicals when exposed to radiation can be used. Preferred photoinitiators include IRGACURE™ 184; acylphosphine oxides such as IRGACURE™ 819; benziketal such as IRGACURE™ 651 available from BASF; benzophenone such as ADDITOL® BP available from allnex, IRGACURE™ 1173, and IRGACURE™ BP available from BASF or Speedcure photoinitiators from Lambson Ltd.

[0063] When present, the amount of photoinitiator in the composition of the second aspect is typically from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, and more preferably from 0.1 to 5% by weight based on the total weight of the composition.

[0064] In other embodiments, the composition includes a free radical generator. Preferably, the free radical generator is present in an amount of 0.01 to 5 wt%, preferably 0.1 to 4 wt%, more preferably 0.2 to 3 wt% based on the total weight of the curable composition (I). Examples of free radical generators are peroxides and azo-type initiators. Examples of peroxide initiators include diacyl peroxides, hydroperoxides, ketone peroxides, peroxy esters, peroxy ketals, dialkyl peroxides, alkyl peresters, and percarbonates, which are used alone or in combination with a redox system. Examples of these peroxides include methyl ethyl ketone peroxide (MEKP), methyl isobutyl ketone peroxide (MIBK), benzoyl peroxide (BPO), and cumene hydroperoxide (CHP). The resin may be cured using a combination of two or more peroxides. Examples of azo-type initiators include azobisisobutyronitrile (AIBN) and related compounds.

[0065] The composition usually includes an inhibitor. Examples of suitable inhibitors include, but are not limited to, phenolic inhibitors such as hydroquinone (HQ), methylhydroquinone (THQ), tert-butylhydroquinone (TBHQ), para-benzoquinone (BQ), 4-tert butylcatechol, di-tert-butylhydroquinone (DTBHQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-tert-butyl-4-methylphenol (BHT), etc. Also included can be phosphines such as triphenylphosphine (TPP), and other substances such as tris-nonylphenyl phosphite (TNPP), phenothiazine (PTZ), and triphenylantimony (TPS). When present, the inhibitor is preferably present in an amount of up to 0.5 wt% of the composition, particularly 0.0001 to 0.2 wt%, preferably 0.01 to 0.1 wt%.

[0066] Light stabilizers can be classified as radical scavengers known as UV absorbers (UVA), quenchers, hydroperoxide decomposers, and hindered amine light stabilizers (HALS).

[0067] In several embodiments, the composition may further comprise a UV absorber and / or a hindered amine light stabilizer. UVA protects the polymer by absorbing destructive UV radiation, while the HALS substance protects by reacting with free radicals generated after high-energy UV photons break chemical bonds within the polymer.

[0068] Examples of UVA are benzotriazoles such as Tinuvin® 328, Tinuvin® 1130, Tinuvin® 900, Tinuvin® 99-2, and Tinuvin® 384-2, triazines such as Tinuvin® 400, Tinuvin® 405, Tinuvin® 460, Tinuvin® 477, and Tinuvin® 479, and benzophenones such as Tinuvin® 531.

[0069] Examples of HALS are Tinuvin® 123, Tinuvin® 144, and Tinuvin® 292, 2,2,6,6-tetramethylpiperidine and 2,6-di-tert-butylpiperidine.

[0070] When present, the light stabilizer may be used in an amount of 0.1 to 5.0, preferably 0.5 to 2.5 weight % of the composition.

[0071] The composition may further comprise additional additives such as fiber wetting agents such as functionalized silanes; and (acidic) adhesion promoters.

[0072] In a second aspect, the present invention relates to a composite material comprising a radiation and / or thermosetting composition according to the first aspect of the present invention and a filler (II).

[0073] In one embodiment, the composite material comprises various amounts of filler material (II), for example up to 95, 90, 80, 70, 60 weight percent of the filler material considering the entire composite material. Suitable filler materials include glass fibers, carbon fibers (including graphite fibers), synthetic polymer fibers (e.g., polyester fibers, polyaramid fibers, polyamide fibers), inorganic fibers (e.g., boron fibers), metal fibers (e.g., steel fibers), carbon nanotubes, mineral nanotubes, etc. Composites based on carbon fibers and polyaramid fibers are typically thermoset.

[0074] In a third aspect, the present invention is directed to: · a step of bringing a filler material into contact with the curable composition (I) of the first aspect; · a step of curing the curable composition (I) in contact with the filler material relates to a method for producing a composite material comprising.

[0075] In the presence or absence of a liner, for filament winding, pultrusion, pull winding, mandrel wrapping, wet lay-up or resin transfer molding, vacuum bagging, vacuum infusion, resin infusion, etc., the composite material according to the present invention can be used.

[0076] The curable composition (I) can also be used to create a conductive sleeve such as a glass fiber reinforced conductive printed sleeve. In this case, the radiation curable composition (I) may be brought into contact with conductive nanoparticles such as carbon nanotubes before or during contact with the filler material (II).

[0077] The present invention is illustrated by the following non-limiting examples.

Examples

[0078] The following examples illustrate aspects and embodiments of the present invention.

[0079] Throughout the present invention, particularly in the examples, the following measurement methods were applied:

[0080] Viscosity: It is the cone plate viscosity at a given temperature, usually 25 °C, and a given rotational speed of the spindle, and is also called shear rate.

[0081] Glass transition temperature (Tg) by DMA (ASTM E1640): The glass transition temperature (Tg) was determined using dynamic mechanical thermal analysis (DMTA, instrument DMA800, TA Instruments) in the three-point bending mode. The span between the support points was 20 mm, and small beam-shaped samples of appropriate dimensions (30 mm × 5 mm × 1.6 mm) were subjected to analysis.

[0082] The vibration frequency of the vibration deformation was 1 Hz, and the amplitude was usually 50 μm. The heating rate was 3 °C / min. The glass transition temperature (Tg) is reported at the temperature of the maximum loss factor (T g = T(tanδ max ))。

[0083] Tensile properties: Ultimate elongation: This ultimate elongation was tested according to ASTM D638 using a Zwick Z010 extensometer equipped with a 500 N load cell. Dogbone-shaped samples with a thickness of 1.7 mm and a width of 3 mm were used as test pieces. The nominal clamping distance was 30 mm. The test was carried out at 23 °C and a crosshead speed of 50 mm / min.

[0084] Flexural modulus, strength and strain - three-point bending test (ASTM D790): The flexural properties are reported at 23 °C and 30% RH and are determined according to the three-point bending test using a Universal Testing Machine Z10 (Zwick) equipped with a 500 N load cell. The span between the supports of the bending fixture was 40 mm, and samples of appropriate dimensions (i.e., 80 mm × 20 mm × 2 mm) were used for the test. The load was applied to the center of the sample at a constant crosshead speed of 2 mm / min. The ultimate flexural strength and strain at break are reported. Calculation of flexural strain: εf = 6Dd / L 2 (where L = support span (mm), d = depth or thickness of the tested beam (mm), D = maximum deflection at the center of the beam (mm))

[0085] Warm water / saline resistance: The glass transition temperature (Tg) and flexural properties are measured after 10 days at 23 °C and 30% relative humidity (RH) and after 10 days in 28% NaCl solution at 80 °C, respectively. The smaller the difference (expressed as %), the better the saline resistance.

[0086] Materials: [Table 1] [Table 2] Table 2 provides a summary of various compositions (EX) and comparative compositions (Com) according to the present invention.

[0087] Results: [Table 3]

[0088] Comparative Example Com1 is an example according to International Publication No. WO 2014 / 191308, and the composition does not contain the structural compound A and provides a composition having insufficient ultimate elongation after curing, so this composition is not suitable for many composite applications.

[0089] Examples 1-6, 9, and 10 are compositions according to the present invention and contain compound B having a cyclic structure, compound A having a structure, and monomer C. All of these have high Tg, good to very good ultimate elongation, and are very flexible. In particular, it is not easy to obtain a composition having a combination of high Tg and good ultimate elongation.

[0090] Comparative Example Com5 shows an example described in International Publication No. WO 2019 / 104079, and this composition contains a high amount of monoacrylate EHMA having a Tg of its homopolymer below -10 °C. As a result, since the Tg is only 75 °C, it becomes a composition not suitable for high heat-resistant composites.

[0091] Results of UV curing and saline analysis

Table 4

[0092] Table 4 shows that the compositions according to the invention (EX7 and EX8) are able to maintain a high Tg, ultimate flexural strain and ultimate elongation even after the cured composition has been brought into contact with the harsh conditions of salt water at elevated temperature for 10 days. Comparative example Com4 does not provide good results because the amount of structural compound A is too low.

[0093] Comparative examples Com2 and Com3 are diluted using monomers having two or more acrylate groups. As a result, compositions are provided that have resins with low performance in terms of low ultimate elongation and / or low ultimate flexural strain.

Claims

1. (A) at least 20% by weight of a compound A comprising at least two ethylenically unsaturated moieties and a structural moiety selected from the group consisting of polyalkylene glycol; polycaprolactone; polybutadiene or hydrogenated or partially hydrogenated forms thereof; polyisoprene or hydrogenated or partially hydrogenated forms thereof; and / or a polyester derivable from a polyol and a dicarboxylic acid; (B) at least 20% by weight of a compound B comprising at least two ethylenically unsaturated moieties and an alicyclic or heterocyclic aliphatic structure; (C) 1 to 40% by weight of a compound C, different from compounds A and B, containing essentially one ethylenically unsaturated moiety and having a viscosity measured at 25°C of less than 100 mPa·s, preferably less than 50 mPa·s, and even more preferably less than 25 mPa·s; and (D) 0 to 20% by weight of a compound D containing at least one ethylenically unsaturated moiety and different from compounds A, B, and C. An actinic radiation curable and / or thermosetting composition (I) for a composite material, comprising: the sum of compounds B and A has a content of 60 to 99% by weight based on the total content of compounds A, B, C and optionally D; A curable composition (I) that, after curing, has a Tg of at least 90° C. according to standard test method ASTM E1640 using dynamic mechanical analysis.

2. The curable composition (I) according to claim 1, wherein the structural portion of compound A is derived from a compound having a Tg of less than 0°C, preferably less than -20°C, more preferably less than -30°C, and even more preferably less than -40°C.

3. The structural part of compound A is condensation reaction of linear aliphatic dicarboxylic acids having 4 to 14 carbon atoms with aliphatic or cycloaliphatic polyols, preferably aliphatic or cycloaliphatic diols; Condensation reaction of dimerized fatty acid compounds with aliphatic or cycloaliphatic diols; or Condensation reaction of dimerized fatty alcohol compounds with aliphatic diacid compounds is a polyester that can be derived from The curable composition (I) according to claim 1.

4. The structural portion of compound A is: a polyalkylene glycol moiety having the structure -((CH2)nO)x- or -(CH2CH(CH3)O)x-; where n is an integer from 2 to 5 and x is an integer from 5 to 20; a polycaprolactone moiety having the structure -(C(C=O)(CH2)uO)t-; where u is an integer from 3 to 5 and t is an integer from 4 to 20; a polybutadiene moiety having the structure -(CH2-CH(CH=CH2)p-(CH2-CH=CH-CH2)q-; where the sum of p and q is an integer from 10 to 100, p≧0, q≧0, or a hydrogenated or partially hydrogenated form thereof; a polyisoprene moiety having the structure -(CH2-C(CH3)=CH-CH2)r-, where r is an integer from 10 to 100, or a hydrogenated or partially hydrogenated form thereof; or ・Structure-(O(C=O)-R'-(C=O)OR"-)n- where R' is a saturated linear alkyl having 2 to 14 carbon atoms, R" is a saturated aliphatic or alicyclic alkyl, and n is an integer from 3 to 20. where R' is a dimerized fatty acid residue; R" is a saturated aliphatic or alicyclic alkyl; and n is an integer from 3 to 20; or wherein R' is an aliphatic diacid residue; R" is a dimerized fatty diol residue; and n is an integer from 3 to 20. The curable composition (I) according to claim 1,

5. The curable composition (I) according to claim 1, wherein the weight average molecular weight of compound A is 200 to 10,000, more preferably 400 to 5,000.

6. 2. The curable composition (I) according to claim 1, wherein compound A is a polyester di- or tri-(meth)acrylate or a polyurethane di- or tri-(meth)acrylate.

7. 2. The curable composition (I) of claim 1, wherein compound B comprises at least two ethylenically unsaturated moieties and preferably no more than eight, more preferably no more than six ethylenically unsaturated moieties.

8. The curable composition (I) according to claim 1, wherein compound B does not contain a structural moiety of compound A.

9. at least 20% by weight of compound A, preferably 20% to 79% by weight, more preferably 20% to 40% by weight of compound A; and at least 20% by weight of compound B, preferably 20% to 79% by weight, more preferably 20% to 50% by weight of compound B 2. The curable composition (I) according to claim 1, comprising: the sum of compounds B and A has a content of 60 to 99% by weight based on the total content of compounds A, B, C and optionally D, Curable composition (I).

10. 2. The curable composition (I) according to claim 1, wherein compound C is added in an amount to obtain a viscosity, measured at 25°C, of ​​less than 2500, preferably less than 1800, more preferably less than 1500 mPa.s.

11. 2. The curable composition (I) according to claim 1, further comprising 0.01 to 10 wt. %, preferably 0.1 to 8 wt. %, more preferably 0.1 to 5 wt. % of a photoinitiator, relative to the total weight of the composition.

12. 2. The curable composition (I) according to claim 1, further comprising 0.01 to 5 wt. %, preferably 0.1 to 4 wt. %, more preferably 0.2 to 3 wt. % of a free radical generator, relative to the total weight of the composition.

13. 2. The curable composition (I) of claim 1, having an ultimate tensile elongation of greater than 3% as measured according to ASTM D638 and / or an ultimate flexural strain of greater than 5% as measured according to standard test method ASTM D790.

14. A composite material comprising the curable composition (I) according to any one of claims 1 to 13 and a filler material (II).

15. 15. A composite material comprising the curable composition (I) of claim 14, wherein the filler material (II) is glass fiber, carbon fiber, synthetic polymer fiber, inorganic fiber, metal fiber, carbon nanotube, or mineral nanotube.

16. - contacting a filling material (II) according to claim 14 with a curable composition (I) according to any one of claims 1 to 13; - curing the curable composition (I) in contact with the filler material (II); A method for making a composite material, comprising:

17. Use of the curable composition (I) according to any one of claims 1 to 13 for filament winding, pultrusion, pull winding, mandrel wrapping, wet lay-up, resin transfer molding, vacuum bagging, vacuum infusion, or resin infusion, with or without a liner.

18. 14. Use of the curable composition (I) according to any one of claims 1 to 13 for producing a conductive sleeve, wherein the curable composition (I) is contacted with conductive nanoparticles before or during contact with the filler material (II).