阅读说明：本技术 用于具有高折射率和具有高热挠曲温度的涂料和材料的具有低粘度的可交联组合物 (Crosslinkable compositions with low viscosity for coatings and materials with high refractive index and high heat deflection temperature ) 是由 G.蒙尼尔 于 2019-09-09 设计创作，主要内容包括：本发明涉及可交联组合物,其包括：组分a)至少一种卤代双酚A二缩水甘油基醚四(甲基)丙烯酸酯,和组分b)来自包含联苯结构的一元醇的单(甲基)丙烯酸酯的至少一种稀释剂,以及来自组分c)、d)、e)、f)和g)的至少一种任选组分。本发明还涉及其用于涂料或材料、特别地用于光学应用的3D打印制品的用途,并且本发明还涉及交联的组合物和成品、特别地由其得到的3D制品。(The present invention relates to a crosslinkable composition comprising: component a) at least one halogenated bisphenol A diglycidyl ether tetra (meth) acrylate, and component b) at least one diluent from mono (meth) acrylates of monoalcohols comprising biphenyl structures, and at least one optional component from components c), d), e), f) and g). The invention also relates to the use thereof for coatings or materials, in particular for 3D printed articles for optical applications, and to crosslinked compositions and finished products, in particular 3D articles obtained therefrom.)

1. A crosslinkable composition, characterized in that it comprises: component a) at least one halogenated bisphenol A diglycidyl ether tetra (meth) acrylate and component b) at least one diluent from mono (meth) acrylates of monoalcohols comprising a biphenyl structure, the biphenyl optionally being halogenated,

and optionally at least one component selected from components c), d), e), f) and g) or combinations thereof as defined below:

c) at least one (meth) acrylated oligomer carrying at least 4 (meth) acrylate functional groups per chain, said oligomer comprising at least 2 halogenated bisphenol A structural units in the oligomer chain,

d) at least one bis (meth) acrylate of an epoxidized biphenyl derivative, said biphenyl optionally being halogenated,

e) optionally halogenated bisphenol A diglycidyl ether bis (meth) acrylate,

f) at least one monomer other than a), b), d) and e),

g) at least one oligomer from the group consisting of urethane (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates.

2. Composition according to claim 1, characterized in that the oligomer as defined according to c) comprises 2 halogenated bisphenol a structural units in the oligomer chain.

3. Composition according to claim 1 or 2, characterized in that the bis (meth) acrylate of the epoxidized biphenyl derivative as defined according to d) is 2-biphenylglycidyl ether bis (meth) acrylate.

4. Composition according to any one of claims 1 to 3, characterized in that the monomer as defined according to f) has a (meth) acrylate functionality ranging from 1 to 6 and is preferably selected from: mono (meth) acrylates of C1-C18 aliphatic alcohols or C6 to C18 cycloaliphatic alcohols, or polyfunctional (meth) acrylates (of functionality 2-6) of C2-C18 polyols, in particular of C3-C18 polyols, or hydroxyalkyl (meth) acrylates, in particular hydroxy (C2-C6 alkyl) esters, (epoxy) acrylates, aminoacrylates and urethane (meth) acrylates, and optionally the monomer f) comprises at least one alkoxy structural unit.

5. Composition according to any one of claims 1 to 4, characterized in that the monomer as defined according to f) comprises one or more alkoxy units, preferably selected from ethoxy, propoxy or butoxy groups or mixtures thereof.

6. Composition according to any one of claims 1 to 5, characterized in that the oligomer of the urethane (meth) acrylate, polyester (meth) acrylate or polyether (meth) acrylate in component g) has a (meth) acrylate functionality in the range of 1 to 15.

7. The composition according to any one of claims 1 to 6, characterized in that the halogenated or optionally halogenated component comprises a halogen selected from bromine, chlorine and fluorine and preferably bromine.

8. Composition according to any one of claims 1 to 7, characterized in that the halogenated or optionally halogenated compound has a number of hydrogen atoms substituted by halogen of the aromatic nucleus of the halogenated or optionally halogenated compound which varies from 1 per aromatic nucleus of the halogenated or optionally halogenated component to 2 per aromatic nucleus of the halogenated or optionally halogenated component, and preferably said number is 2 hydrogen atoms substituted by halogen per aromatic nucleus of the component.

9. Composition according to any one of claims 1 to 8, characterized in that the component a) is tetrabromobisphenol A diglycidyl ether tetramethacrylate of formula (I) below:

10. composition according to any one of claims 1 to 9, characterized in that the component b) is a biphenyl carbinol mono (meth) acrylate of formula (II):

wherein R is methyl or H, preferably H.

11. Composition according to any one of claims 1 to 10, characterized in that the oligomer as defined according to c) has the following formula (III):

12. composition according to any one of claims 1 to 11, characterized in that the monomer d) is 2-biphenylglycidyl ether dimethacrylate as defined according to the following formula (IVc):

13. composition according to any one of claims 1 to 12, characterized in that the content by weight of component a) with respect to the weight of a) + b) varies from 20% to 80%, preferably from 35% to 65%.

14. Composition according to one of claims 1 to 13, characterized in that the content by weight of component c) with respect to the weight of a) + b) varies from 0% to 50%, preferably from 5% to 35%.

15. Composition according to any one of claims 1 to 14, characterized in that the content by weight of component d) with respect to the weight a) + b) varies from 0% to 50%, preferably from 5% to 35%.

16. Composition according to any one of claims 1 to 15, characterized in that the content by weight of component e) with respect to the weight a) + b) varies from 0% to 50%, preferably from 5% to 30%.

17. Composition according to any one of claims 1 to 16, characterized in that the content by weight of f) with respect to the weight of a) + b) varies from 0% to 50%, preferably from 5% to 35%.

18. Composition according to any one of claims 1 to 17, characterized in that the content by weight of g) with respect to the weight of a) + b) varies from 0% to 40%, preferably from 10% to 30%.

19. Composition according to any one of claims 1 to 18, characterized in that it comprises, in addition to a) and b) and optionally c) to g), at least one initiator.

20. Composition according to any one of claims 1 to 19, characterized in that it comprises an initiator chosen from peroxides or hydroperoxides and is capable of crosslinking by a thermal route or at low temperatures in the presence of a reduction promoter for said peroxides or hydroperoxides.

21. Composition according to any one of claims 1 to 19, characterized in that it comprises as at least one photoinitiator an initiator and is capable of being crosslinked by UV radiation, including near UV/visible radiation, preferably by a UV/visible lamp, by a laser or by an LED.

22. Composition according to any one of claims 1 to 19, characterized in that it does not comprise any initiator and in that it is capable of being crosslinked by EB (electron beam) radiation.

23. Composition according to any one of claims 1 to 19, characterized in that it can be crosslinked by a dual route combining at least two crosslinking techniques as defined in any one of claims 20 to 22.

24. Composition according to any one of claims 1 to 23, characterized in that it has a viscosity at 25 ℃ according to the ISO3219(1993) method of less than 5000mpa.s, and preferably less than 2500mpa.s, more preferably less than 1500 mpa.s.

25. Composition according to any one of claims 1 to 24, characterized in that it has, after crosslinking, an HDT according to the method of ISO 75(2004) of at least 70 ℃ and preferably greater than 80 ℃.

26. Composition according to any one of claims 1 to 25, characterized in that it has, after crosslinking, a young's modulus at 25 ℃ according to the method of ISO 527(1995) of at least 1800MPa, preferably at least 2000 MPa.

27. Composition according to any one of claims 1 to 26, characterized in that it has an RI according to the ASTM 1218-02 standard of at least 1.47, preferably greater than 1.52 and more particularly greater than 1.56 before crosslinking and at least 1.50, and preferably greater than 1.55 and more particularly greater than 1.59 after crosslinking.

28. Use of a composition according to any one of claims 1 to 27 for the preparation of a coating or material having an HDT according to the method of ISO 75(2004) of at least 70 ℃ and preferably greater than 80 ℃ and/or an RI of at least 1.50, preferably greater than 1.55 and more particularly greater than 1.59.

29. Use according to claim 28, characterized in that the material is a 3D printed article or a material different from a 3D printed article.

30. Use according to claim 28 or 29, characterized in that it relates to a 3D printed article.

31. Use according to claim 30, characterized in that it relates to a 3D printed article printed by a layer-by-layer printing process or by a continuous process.

32. Use according to any one of claims 29 to 31, characterized in that it relates to a 3D printed article having a refractive index RI of at least 1.50, preferably greater than 1.55 and more particularly greater than 1.59.

33. Use according to any one of claims 29 to 32, characterized in that it relates to optical applications, and preferably for:

plastic lenses, in particular spectacle lenses, digital camera lenses or optical prism lenses, or

Optical coatings in optical overcoatings, hard optical coatings or antireflection films or for coating of LEDs or solar (photovoltaic) cells, or

Optical fibers, holograms, lenses for prisms and LED materials.

34. A crosslinked composition, characterized in that it results from the crosslinking of at least one composition as defined according to any one of claims 1 to 27.

35. A finished product, characterized in that it results from the crosslinking of at least one composition as defined according to any one of claims 1 to 27, or that it comprises at least one crosslinked composition as defined according to claim 34.

36. The finished product according to claim 35, characterized in that it is: a coating, a shaped material, in particular a composite material, or a 3D printed article.

37. The finished product according to claim 36, characterized in that it is a 3D printed article, preferably selected from:

plastic lenses, in particular spectacle lenses, digital camera lenses or optical prism lenses, or

Optical coatings in optical overcoatings, hard optical coatings or antireflection films or for coating of LEDs or solar (photovoltaic) cells, or

Optical fibers, holograms, lenses for prisms and LED materials.

Examples

1)Formulations

The compositions of the formulations tested according to examples 1-5 are listed in table 1 below, starting with the following components:

a compound A: SR833S, Sartomer, Dicyclodecane dimethanol diacrylate

Compound B: tetrabromobisphenol A diglycidyl ether dimethacrylate

Compound C: tetrabromobisphenol A diglycidyl ether tetramethyl acrylate

Compound D: biphenyl glycidyl ether dimethacrylate

Compound E: SR348L from Sartomer, bisphenol A ethoxylate (2) bis methacrylate

Compound F: HPMA, hydroxypropyl methacrylate from Evonik

Compound G: h008, Biphenylcarbinol acrylate from KPX Green Chemical

TABLE 1: compositions of the tested formulations of examples 1-5

Components	Example 1	Example 2	Example 3	Example 4	Example 5
						A	14.0	/	/	13.30	/
B	27.0	12.50	13.20	25.65	/
						C	27.0	29.25	30.85	25.65	42.75
D	/	/	/	/	23.75
						E	/	16.75	17.70	/	/
F	/	10.0	5.0	5.0	5.0
						G	32.0	31.5	33.25	30.40	28.50
In total:	100.0	100.0	100.0	100.0	100.0

2) characterization of liquid formulations before crosslinking

These properties are listed in table 2 below.

TABLE 2: properties of the formulations tested in examples 1 to 5

3) Physicochemical Properties after Cross-linking

Sample (I)

Samples were prepared starting from silicone (silica gel) molds. The strips (DMA, HDT, 3-point bend) had dimensions in mm of 80 x 10 x 4 and the type 5A test specimens used for the tensile test had a thickness of 4 mm. The photoinitiator system for all formulations was TPO-L, 2%, and crosslinking was performed under a 100% UV benchmark (bench top) LED tape, followed by post-curing at 80 ℃ for 12 hours.

Analysis conditions were as follows:

the test was carried out at 23 ℃ at 50% relative humidity.

-DMA analysis:

the DMA analysis was performed on a RDAIII apparatus (Rheometrics) with a rectangular twist under scanning from-50 ℃ to 200 ℃ at 3 ℃/min and 0.05% nominal strain and at a frequency of 1 Hz.

HDT (standard ISO 75 in 2004):

HDT (heat deflection temperature) tests were performed on HDT devices (EDIT). Method A (1.8MPa) is adopted; the sample (thickness 4mm) was laid flat on a substrate (distance between supports: 64 mm). The heating rate was 120 ℃/h.

-tensile test:

the tensile test was performed on an MTS tensile test apparatus 500N cell. The sample used was type 5A. The pull rate was 1 mm/min and from 7% elongation then 10 mm/min.

-3-point bending (2001 standard ISO 178)

The 3-point bend test was conducted in a 3-point bend mode on an MTS tensile testing apparatus with a distance between supports of 16x the average thickness of the batch (batch). The test rate was 1 mm/min.

Results

The performance quality results for the tested formulations of examples 1-5 are set forth in table 3 below.

TABLE 3: performance qualities of the tested formulations of examples 1-5